Abstract Book - International Symposium on Molecular Spectroscopy

Transcription

MA. Plenary
1
Monday, June 22, 2015 – 8:30 AM
Room: Foellinger Auditorium
Chair: Gregory S. Girolami, University of Illinois at Urbana-Champaign, Urbana, IL, USA
8:30
ar
y
Welcome
Phyllis M. Wise, Chancellor
University of Illinois at Urbana-Champaign
MA01
8:40 – 9:20
BREATHING EASIER THROUGH SPECTROSCOPY: STUDYING FREE RADICAL REACTIONS IN AIR POLLUTION
CHEMISTRY, Mitchio Okumura
MA02
9:25 – 10:05
MOLECULAR ROTATION SIGNALS: MOLECULE CHEMISTRY AND PARTICLE PHYSICS, Jens-Uwe Grabow
Intermission
in
MA03
10:35 – 11:15
IT IS WATER WHAT MATTERS: THz SPECTROSCOPY AS A TOOL TO STUDY HYDRATION DYNAMICS,
Martina Havenith
Pr
el
im
MA04
11:20 – 12:00
CPUF: CHIRPED-PULSE MICROWAVE SPECTROSCOPY IN PULSED UNIFORM SUPERSONIC FLOWS,
Arthur Suits, Chamara Abeysekera, Lindsay N. Zack, Baptiste Joalland, Nuwandi M Ariyasingha, Barratt Park, Robert W
Field, Ian Sims
2
MF. Mini-symposium: High-Precision Spectroscopy
Monday, June 22, 2015 – 1:30 PM
Room: 116 Roger Adams Lab
Chair: Michael Heaven, Emory University, Atlanta, GA, USA
ar
y
MF01
Journal of Molecular Spectroscopy Review Lecture
1:30 – 2:00
PHYSICS BEYOND THE STANDARD MODEL FROM MOLECULAR HYDROGEN SPECTROSCOPY, Wim Ubachs,
Edcel John Salumbides, Julija Bagdonaite
MF02
PRECISION SPECTROSCOPY ON HIGHLY-EXCITED VIBRATIONAL LEVELS OF H2 ,
Edcel John Salumbides, Wim Ubachs
2:05 – 2:20
Ming Li Niu,
MF03
2:22 – 2:37
BOUNDS ON THE NUMBER AND SIZE OF EXTRA DIMENSIONS FROM MOLECULAR SPECTROSCOPY,
Edcel John Salumbides, Bert Schellekens, Beatriz Gato-Rivera, Wim Ubachs
in
MF04
2:39 – 2:54
CONTINUOUS SUPERSONIC EXPANSION DISCHARGE SOURCE FOR HIGH-PRECISION MID-INFRARED SPECTROSCOPY OF COLD MOLECULAR IONS, Courtney Talicska, Michael Porambo, Benjamin J. McCall
MF05
2:56 – 3:11
PROGRESS TOWARDS A HIGH-PRECISION INFRARED SPECTROSCOPIC SURVEY OF THE H+
ION,
3
Adam J. Perry, James N. Hodges, Charles R. Markus, G. Stephen Kocheril, Paul A. Jenkins II, Benjamin J. McCall
Intermission
Pr
el
im
MF06
3:30 – 3:45
HIGH PRECISION INFRARED SPECTROSCOPY OF OH+ , Charles R. Markus, Adam J. Perry, James N. Hodges, G.
Stephen Kocheril, Paul A. Jenkins II, Benjamin J. McCall
MF07
3:47 – 4:02
TOWARD TWO-COLOR SUB-DOPPLER SATURATION RECOVERY KINETICS IN CN (X, v = 0, J), Hong Xu, Damien
Forthomme, Trevor Sears, Gregory Hall, Paul Dagdigian
MF08
4:04 – 4:19
AN EMPIRICAL DIPOLE POLARIZABILITY FOR He FROM A FIT TO SPECTROSCOPIC DATA YIELDING ANALYTIC EMPIRICAL POTENTIALS FOR ALL ISOTOPOLOGUES OF HeH+ , Young-Sang Cho, Robert J. Le Roy, Nikesh
S. Dattani
MF09
4:21 – 4:36
ANALYTIC EMPIRICAL POTENTIALS FOR BeH+ , BeD+ , AND BeT+ INCLUDING UP TO 4TH ORDER QED
IN THE LONG-RANGE, AND PREDICTIONS FOR THE HALO NUCLEONIC MOLECULES 11 BeH+ and 14 BeH+ .,
Lena C. M. Li Chun Fong, Grzegorz Lach, Robert J. Le Roy, Nikesh S. Dattani
MF10
4:38 – 4:53
ANALYTIC EMPIRICAL POTENTIAL AND ITS COMPARISON TO STATE OF THE ART ab initio CALCULATIONS
FOR THE 6e− EXCITED b(13 Πu )-STATE OF Li2 ., Nikesh S. Dattani, Robert J. Le Roy
MF11
4:55 – 5:10
PRECISION SPECTROSCOPY OF TRAPPED HfF+ WITH A COHERENCE TIME OF 1 SECOND, Kevin Cossel, William
Cairncross, Matt Grau, Dan Gresh, Yan Zhou, Jun Ye, Eric Cornell
MF12
5:12 – 5:27
BROADBAND FREQUENCY COMB AND CW-LASER VELOCITY MODULATION SPECTROSCOPY OF ThF+ ,
Dan Gresh, Kevin Cossel, Jun Ye, Eric Cornell
MF13
5:29 – 5:44
PURE MW DATA FOR v = 0 − 6 OF PbI GIVE VIBRATIONAL SPACINGS AND A FULL ANALYTIC POTENTIAL
ENERGY FUNCTION, Ji Ho (Chris) Yoo, Corey Evans, Nick Walker, Robert J. Le Roy
3
MG. Structure determination
Monday, June 22, 2015 – 1:30 PM
Room: 100 Noyes Laboratory
Chair: Ha Vinh Lam Nguyen, Université Paris-Est Créteil, Créteil, France
1:30 – 1:45
CHEMISTRIES,
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y
MG01
DETECTION OF HSNO, A CRUCIAL INTERMEDIATE LINKING NO AND H2 S
Marie-Aline Martin-Drumel, Carrie Womack, Kyle N Crabtree, Sven Thorwirth, Michael C McCarthy
MG02
1:47 – 2:02
DETECTION AND STRUCTURAL CHARACTERIZATION OF NITROSAMIDE H2 NNO: A CENTRAL INTERMEDIATE IN deNOx PROCESSES, Michael C McCarthy, Kelvin Lee, John F. Stanton
MG03
2:04 – 2:19
MICROWAVE SPECTRA OF 1- AND 2-BROMOBUTANE, Soohyun Ka, Jihyun Kim, Heesu Jang, JUNG JIN Oh
in
MG04
2:21 – 2:36
ACCURATE EQUILIBRIUM STRUCTURES FOR trans-HEXATRIENE BY THE MIXED ESTIMATION METHOD AND
FOR THE THREE ISOMERS OF OCTATETRAENE FROM THEORY; STRUCTURAL CONSEQUENCES OF ELECTRON DELOCALIZATION, Norman C. Craig, Jean Demaison, Peter Groner, Heinz Dieter Rudolph, Natalja Vogt
MG05
2:38 – 2:53
RING PUCKERING POTENTIALS OF THREE FLUORINATED CYCLOPENTENES: C5 F8 , C5 HF7 , and C5 H2 F6 ,
E. A. Arsenault, B. E. Long, Wallace C. Pringle, Yoon Jeong Choi, S. A. Cooke, Esther J Ocola, Jaan Laane
Pr
el
im
MG06
2:55 – 3:10
CONFORMATIONAL TRANSFORMATION OF FIVE-MEMBERED RINGS: THE GAS PHASE STRUCTURE OF 2METHYLTETRAHYDROFURAN, Vinh Van, Ha Vinh Lam Nguyen, Wolfgang Stahl
MG07
3:12 – 3:27
ASSIGNMENT OF THE MICROWAVE SPECTRUM OF 1,2-DIFLUOROBENZENE· · · HCCH: LESSONS LEARNED
FROM ANALYSIS OF A DENSE BROADBAND SPECTRUM, Anuradha Akmeemana, Rebecca D. Nelson, Mikayla L.
Grant, Rebecca A. Peebles, Sean A. Peebles, Justin M. Kang, Nathan A Seifert, Brooks Pate
MG08
3:29 – 3:39
STRUCTURE DETERMINATION AND CH· · · F INTERACTIONS IN H2 C=CHF· · · H2 C=CF2 BY FOURIERTRANSFORM MICROWAVE SPECTROSCOPY, Rachel E. Dorris, Rebecca A. Peebles, Sean A. Peebles
Intermission
MG09
3:58 – 4:13
MILLIMETER WAVE SPECTROSCOPY AND EQUILIBRIUM STRUCTURE DETERMINATION OF PYRIMIDINE (mC4 H4 N2 ), Zachary N. Heim, Brent K. Amberger, Brian J. Esselman, R. Claude Woods, Robert J. McMahon
MG10
4:15 – 4:30
MILLIMETER-WAVE SPECTROSCOPY OF PHENYL ISOCYANATE, Cara E. Schwarz, Brent K. Amberger, Benjamin C.
Haenni, Brian J. Esselman, R. Claude Woods, Robert J. McMahon
MG11
4:32 – 4:47
BROADBAND MICROWAVE SPECTROSCOPY AS A TOOL TO STUDY THE STRUCTURES OF ODORANT
MOLECULES AND WEAKLY BOUND COMPLEXES IN THE GAS PHASE , Sabrina Zinn, Thomas Betz, Chris Medcraft, Melanie Schnell
MG12
4:49 – 5:04
MICROWAVE SPECTRA OF 9-FLUORENONE AND BENZOPHENONE, Channing West, Galen Sedo, Jennifer van Wijngaarden
MG13
5:06 – 5:21
ASSESSING THE IMPACT OF BACKBONE LENGTH AND CAPPING AGENT ON THE CONFORMATIONAL
PREFERENCES OF A MODEL PEPTIDE: CONFORMATION SPECIFIC IR AND UV SPECTROSCOPY OF 2AMINOISOBUTYRIC ACID, Joseph R. Gord, Daniel M. Hewett, Matthew A. Kubasik, Timothy S. Zwier
MG14
5:23 – 5:38
COMPARISON OF INTRAMOLECULAR FORCES IN DIPEPTIDES WITH TWO AROMATIC RINGS: DOES DISPERSION DOMINATE?, Jessica A. Thomas
4
MH. Linelists
Monday, June 22, 2015 – 1:30 PM
Room: B102 Chemical and Life Sciences
Chair: Shanshan Yu, California Institute of Technology, Pasadena, CA, USA
ar
y
MH01
1:30 – 1:45
HITRAN IN THE XXIst CENTURY: BEYOND VOIGT AND BEYOND EARTH, Laurence S. Rothman, Iouli E Gordon,
Christian Hill, Roman V Kochanov, Piotr Wcislo, Jonas Wilzewski
MH02
1:47 – 2:02
HITRANonline: A NEW STRUCTURE AND INTERFACE FOR HITRAN LINE LISTS AND CROSS SECTIONS , Christian Hill, Laurence S. Rothman, Iouli E Gordon, Roman V Kochanov, Piotr Wcislo, Jonas Wilzewski
MH03
2:04 – 2:19
WORKING WITH HITRAN DATABASE USING HAPI: HITRAN APPLICATION PROGRAMMING INTERFACE,
Roman V Kochanov, Christian Hill, Piotr Wcislo, Iouli E Gordon, Laurence S. Rothman, Jonas Wilzewski
in
MH04
2:21 – 2:31
GPU ACCELERATED INTENSITIES: A NEW METHOD OF COMPUTING EINSTEIN-A COEFFICIENTS,
Ahmed Faris Al-Refaie, Sergei N. Yurchenko, Jonathan Tennyson
Pr
el
im
MH05
2:33 – 2:48
LINE SHAPE PARAMETERS FOR NEAR INFRARED CO2 BANDS IN THE 1.61 AND 2.06 MICRON SPECTRAL
REGIONS, V. Malathy Devi, D. Chris Benner, Keeyoon Sung, Linda Brown, Timothy J Crawford, Mary Ann H. Smith,
Arlan Mantz
MH06
2:50 – 3:05
RELIABLE IR LINE LISTS FOR SO2 AND CO2 ISOTOPOLOGUES COMPUTED FOR ATMOSPHERIC MODELING
ON VENUS AND EXOPLANETS, Xinchuan Huang, David Schwenke, Timothy Lee, Robert R. Gamache
MH07
3:07 – 3:22
LASER SPECTROSCOPIC STUDY OF CaH IN THE B2 Σ+ AND D2 Σ+ STATES, Kyohei Watanabe, Kanako Uchida,
Kaori Kobayashi, Fusakazu Matsushima, Yoshiki Moriwaki
Intermission
MH08
3:41 – 3:56
18
ADDITIONAL MEASUREMENTS AND ANALYSES OF H17
2 O AND H2 O, John Pearson, Shanshan Yu, Adam Walters
MH09
3:58 – 4:13
EXPERIMENTAL LINE LISTS OF HOT METHANE, Robert J. Hargreaves, Peter F. Bernath, Jeremy Bailey, Michael
Dulick
MH10
4:15 – 4:30
EXPERIMENTAL TRANSMISSION SPECTRA OF HOT AMMONIA IN THE INFRARED, Christopher A. Beale, Robert
J. Hargreaves, Michael Dulick, Peter F. Bernath
MH11
4:32 – 4:47
HYPERSONIC POST-SHOCK CAVITY RING-DOWN SPECTROSCOPY, Nicolas Suas-David, Samir Kassi, Abdessamad
Benidar, Robert Georges
MH12
4:49 – 5:04
CH3 D NEAR INFRARED CAVITY RING-DOWN SPECTRUM REANALYSIS AND IR-IR DOUBLE RESONANCE,
Shaoyue Yang, George Schwartz, Kevin Lehmann
MH13
5:06 – 5:21
AYTY: A NEW LINE-LIST FOR HOT FORMALDEHYDE, Ahmed Faris Al-Refaie, Sergei N. Yurchenko, Jonathan Tennyson, Andrey Yachmenev
MH14
5:23 – 5:38
THE MICROWAVE SPECTROSCOPY OF AMINOACETONITRILE IN THE VIBRATIONAL EXCITED STATE, Chiho
Fujita, Hiroyuki Ozeki, Kaori Kobayashi
MI. Ions
5
Monday, June 22, 2015 – 1:30 PM
Room: 274 Medical Sciences Building
Chair: Mark Johnson, Yale University, New Haven, CT, USA
ar
y
MI01
1:30 – 1:45
ROTATIONAL ACTION SPECTROSCOPY VIA STATE-SELECTIVE HELIUM ATTACHMENT, Lars Kluge, Alexander
Stoffels, Sandra Brünken, Oskar Asvany, Stephan Schlemmer
MI02
1:47 – 2:02
SYMMETRY BEYOND PERTURBATION THEORY: FLOPPY MOLECULES AND ROTATION-VIBRATION STATES,
Hanno Schmiedt, Stephan Schlemmer, Per Jensen
MI03
2:04 – 2:19
STUDYING ROTATION/TORSION COUPLING IN H+
USING
DIFFUSION
MONTE
CARLO,
Melanie
L.
Marlett,
Zhou
5
Lin, Anne B McCoy
in
MI04
2:21 – 2:36
HIGH-J ROTATIONAL LINES OF 13 C ISOTOPOLOGUES OF HCO+ MEASURED BY USING EVENSON-TYPE TUNABLE FIR SPECTROMETER, Mari Suzuki, Ryo Oishi, Yoshiki Moriwaki, Fusakazu Matsushima, Takayoshi Amano
MI05
2:38 – 2:48
UV-UV HOLE-BURNING SPECTROSCOPY OF A PROTONATED ADENINE DIMER IN A COLD QUADRUPOLE ION
TRAP, Hyuk Kang
Pr
el
im
MI06
2:50 – 3:05
SPECTROSCOPIC INVESTIGATION OF PROTON-COUPLED ELECTRON TRANSFER IN WATER OXIDATION CATALYZED BY A RUTHENIUM COMPLEX, [Ru(tpy)(bpy)(H2 O)]2+ , Erin M. Duffy, Brett Marsh, Jonathan Voss, Etienne
Garand
MI07
3:07 – 3:22
PROBING SOLVATAION SHELLS OF Ni(H2 O)m 2+ (m=4-10) AND NiOH(H2 O)n + (n=2-5) WITH CRYOGENIC ION
VIBRATIONAL SPECTROSCOPY. , Jonathan Voss, Brett Marsh, Jia Zhou, Etienne Garand
MI08
3:24 – 3:39
MICROSOLVATION OF THE Mg2 SO4 2+ CATION: CRYOGENIC VIBRATIONAL SPECTROSCOPY OF
(Mg2+ )2 SO4 2− (H2 O)n=4−11 , Patrick J Kelleher, Joseph W DePalma, Christopher J Johnson, Joseph Fournier, Mark
Johnson
Intermission
MI09
3:58 – 4:13
CAPTURE AND STRUCTURAL DETERMINATION OF ACTIVATED INTERMEDIATES IN NICKEL CATALYZED
CO2 REDUCTION, Stephanie Craig, Fabian Menges, Arron Wolk, Joseph Fournier, Niklas Tötsch, Mark Johnson
MI10
4:15 – 4:30
THRESHOLD IONIZATION SPECTROSCOPIC CHARACTERIZATION OF La ATOM REACTION WITH ISOPRENE,
Wenjin Cao, Dong-Sheng Yang
MI11
4:32 – 4:47
Ce-PROMOTED BOND ACTIVATION OF ETHYLENE PROBED BY MASS-ANALYZED THRESHOLD IONIZATION
SPECTROSCOPY, Yuchen Zhang, Sudesh Kumari, Wenjin Cao, Dong-Sheng Yang
MI12
4:49 – 5:04
STRUCTURE DETERMINATION OF CISPLATIN-AMINO ACID ANALOGUES BY INFRARED MULTIPLE PHOTON
DISSOCIATION ACTION SPECTROSCOPY, Chenchen He, Xun Bao, Yanlong Zhu, Stephen Strobehn, Bett Kimutai, Y-W
Nei, C S Chow, M T Rodgers, Juehan Gao, J. Oomens
MI13
5:06 – 5:21
STRUCTUAL EFFECTS OF CYTIDINE 2′ RIBOSE MODIFICATIONS AS DETERMINED BY IRMPD ACTION SPECTROSCOPY, Lucas Hamlow, Chenchen He, Lin Fan, Ranran Wu, Bo Yang, M T Rodgers, Giel Berden, J. Oomens
MI14
5:23 – 5:38
GAS-PHASE CONFORMATIONS AND ENERGETICS OF SODIUM CATIONIZED 2′ -DEOXYGUANOSINE AND
GUANOSINE: IRMPD ACTION SPECTROSCOPY AND THEORETICAL STUDIES, Yanlong Zhu, Lucas Hamlow,
Chenchen He, Xun Bao, M T Rodgers, Juehan Gao, J. Oomens
MI15
5:40 – 5:55
UNRAVELING PROTON TRANSFER IN STEPWISE HYDRATED N-HETEROCYCLIC ANIONS, John T. Kelly, Nathan
I Hammer, Kit Bowen, Gregory S. Tschumper
6
MJ. Small molecules
Monday, June 22, 2015 – 1:30 PM
Chair: Leah C O’Brien, Southern Illinois University, Edwardsville, IL, USA
ar
y
MJ01
1:30 – 1:45
DEPERTURBATION ANALYSIS FOR THE a3 Π AND c3 Σ− STATES OF C2 , Jian Tang, Wang Chen, Kentarou Kawaguchi
MJ02
1:47 – 2:02
HIGH – RESOLUTION LASER SPECTROSCOPY OF THE A 3 Π1 ← X 1 Σ+ SYSTEM OF ICl IN 0.7 µm REGION. ,
Nobuo Nishimiya, Tokio Yukiya, Masao Suzuki, Robert J. Le Roy
MJ03
2:04 – 2:19
HIGH RESOLUTION LASER SPECTROSCOPY FOR ABSORPTION TO LEVELS LYING NEAR THE DISSOCIATION
LIMIT OF THE A 3 Π1 STATE OF IBr, Tokio Yukiya, Nobuo Nishimiya, Masao Suzuki, Robert J. Le Roy
in
MJ04
2:21 – 2:36
THE NEAR-INFRARED SPECTRUM OF NiCl: ANALYSES OF THE (0,1), (1,0), & (2,1) BANDS OF SYSTEM G AND
THE (1,0) BAND OF SYSTEM H, Jack C Harms, Courtney N Gipson, Ethan M Grames, James J O’Brien, Leah C O’Brien
MJ05
2:38 – 2:53
ANALYSIS OF EMISSION SPECTRA OF YTTRIUM MONOIODIDE PRODUCED BY THE PHOTODISSOCIATION
OF YI3 , Wenting Wendy Chen, Thomas C. Galvin, Thomas J. Houlahan, Jr., J. Gary Eden
Pr
el
im
MJ06
2:55 – 3:05
GENERATION OF VIBRATIONALLY EXCITED HCP FROM A STABLE SYNTHETIC PRECURSOR,
Alexander W. Hull, Jun Jiang, Trevor J. Erickson, Carrie Womack, Matthew Nava, Christopher Cummins, Robert W
Field
Intermission
MJ07
3:24 – 3:39
DPF ANALYSES YIELD FULLY ANALYTIC POTENTIALS FOR THE B 1 Πu “BARRIER” STATES OF Rb2 and Li2
AND AN IMPROVED GROUND-STATE WELL DEPTH FOR Rb2 , Kai Slaughter, Nikesh S. Dattani, Claude S. Amiot,
Amanda J. Ross, Robert J. Le Roy
MJ08
3:41 – 3:56
LASER SPECTROSCOPY OF THE PHOTOASSOCIATION OF Rb–Ar AND Rb–Kr THERMAL PAIRS: STRUCTURE
OF THE Rb–RARE GAS A2 Π1/2 STATE NEAR THE CLASSICAL LIMIT, Andrey E. Mironov, William Goldshlag, Kyle
T Raymond, J. Gary Eden
MJ09
3:58 – 4:13
COLLISION-INDUCED ABSORPTION WITH EXCHANGE EFFECTS AND ANISOTROPIC INTERACTIONS: THEORY AND APPLICATION TO H2 − H2 and N2 − N2 ., Tijs Karman, Evangelos Miliordos, Katharine Hunt, Ad van der
Avoird, Gerrit Groenenboom
MJ10
Post-Deadline Abstract
4:15 – 4:30
PHOTO-DISSOCIATION RESONANCES OF JET-COOLED NO2 AT THE DISSOCIATION THRESHOLD BY CWCRDS, CHALLENGING RRKM THEORIES, Patrick Dupré
MJ11
4:32 – 4:47
SELF- AND CO2 -BROADENED LINE SHAPE PARAMETERS FOR THE ν2 AND ν3 BANDS OF HDO, V. Malathy Devi,
D. Chris Benner, Keeyoon Sung, Linda Brown, Arlan Mantz, Mary Ann H. Smith, Robert R. Gamache, Geronimo L. Villanueva
MJ12
DISPERSED FLUORESCENCE SPECTRA OF JET COOLED SiCN, Masaru Fukushima, Takashi Ishiwata
4:49 – 5:04
MJ13
5:06 – 5:21
INTERNAL FORCE FIELD DETERMINATION OF C̃1 B2 STATE of SO2 , Jun Jiang, Barratt Park, Carrie Womack, Robert
W Field
MJ14
5:23 – 5:38
MEASUREMENT AND MODELING OF COLD 13 CH4 SPECTRA FROM 2.1 TO 2.7 µm, Linda Brown, Keeyoon Sung,
Timothy J Crawford, Andrei V. Nikitin, Sergey Tashkun, Michael Rey, Vladimir Tyuterev, Mary Ann H. Smith, Arlan Mantz
7
TA. Metal containing
Tuesday, June 23, 2015 – 8:30 AM
Chair: Jacob Stewart, Emory University, Atlanta, GA, USA
ar
y
TA01
8:30 – 8:45
BONDING AT THE EXTREME. DETECTION AND CHARACTERIZATION OF THORIUM DIMER, Th2 ,
Timothy Steimle, Seth Muscarella, Damian L Kokkin
TA02
8:47 – 9:02
THE QUINTESSENTIAL BOND OF MODERN SCIENCE. THE DETECTION AND CHARACTERIZATION OF DIATOMIC GOLD SULFIDE, AuS., Damian L Kokkin, Ruohan Zhang, Timothy Steimle, Bradley W Pearlman, Ian A Wyse,
Thomas D. Varberg
TA03
9:04 – 9:19
LASER SPECTROSCOPY OF RUTHENIUM CONTAINING DIATOMIC MOLECULES: RuH/D AND RuP.,
Allan G. Adam, Ricarda M. Konder, Nicole M. Nickerson, Colan Linton, D. W. Tokaryk
in
TA04
9:21 – 9:36
OPTICAL ZEEMAN SPECTROSCOPY OF CALCIUM FLUORIDE, CaF., Timothy Steimle, Damian L Kokkin, Jack
Delvin, Michael Tarbutt
TA05
9:38 – 9:53
ELECTRONIC TRANSITIONS OF YTTRIUM MONOPHOSPHIDE, Allan S.C. Cheung, Biu Wa Li, MAN-CHOR Chan
Pr
el
im
TA06
ROTATIONALLY RESOLVED SPECTROSCOPY OF THE B 1 Π ← X 1 Σ+ AND C 1 Σ+ ← X 1 Σ+
ELECTRONIC BANDS OF CaO, Michael Sullivan, Jacob Stewart, Michael Heaven
9:55 – 10:10
Intermission
TA07
10:29 – 10:44
HIGH RESOLUTION LASER SPECTROSCOPY OF NICKEL MONOBORIDE, NiB, E. S. Goudreau, Colan Linton, D. W.
Tokaryk, Allan G. Adam
TA08
10:46 – 11:01
MOLECULAR LINE LISTS FOR SCANDIUM AND TITANIUM HYDRIDE USING THE DUO PROGRAM,
Lorenzo Lodi, Sergei N. Yurchenko, Jonathan Tennyson
TA09
11:03 – 11:18
UV SPECTROSCOPY ON GAS PHASE Cu(I)-BIPYRIDYL COMPLEXES , Shuang Xu, Casey Christopher, J. Mathias
Weber
TA10
11:20 – 11:35
ANION PHOTOELECTRON SPECTROSCOPY OF NbW− and W2 − , D. Alex Schnepper, Melissa A. Baudhuin, Doreen
Leopold, Sean M. Casey
8
TB. Mini-symposium: Accelerator-Based Spectroscopy
Chair: Jennifer van Wijngaarden, University of Manitoba, Winnipeg, MB, Canada
ar
y
TB01
INVITED TALK
8:30 – 9:00
JET-COOLED SPECTROSCOPY ON THE AILES INFRARED BEAMLINE OF THE SYNCHROTRON RADIATION
FACILITY SOLEIL, Robert Georges
TB02
9:05 – 9:20
LOWEST VIBRATIONAL STATES OF ACRYLONITRILE, Zbigniew Kisiel, Marie-Aline Martin-Drumel, Olivier Pirali
TB03
9:22 – 9:37
FIR SYNCHROTRON SPECTROSCOPY OF HIGH TORSIONAL LEVELS OF CD3 OH: THE TAU OF METHANOL,
Ronald M. Lees, Li-Hong Xu, Brant E Billinghurst
TB04
9:39 – 9:54
FAR-INFRARED SYNCHROTRON-BASED SPECTROSCOPY OF PROTON TUNNELLING IN MALONALDEHYDE,
E. S. Goudreau, D. W. Tokaryk, Stephen Cary Ross
in
Intermission
TB05
INVITED TALK
10:13 – 10:43
THE DISCRETE NATURE OF THE COHERENT SYNCHROTRON RADIATION, Stefano Tammaro, Olivier Pirali, P. Roy,
Jean François LAMPIN, Gaël DUCOURNEAU, Arnaud Cuisset, Francis Hindle, Gaël Mouret
Pr
el
im
TB06
10:48 – 11:03
LOW-TEMPERATURE COLLISIONAL BROADENING IN THE FAR-INFRARED CENTRIFUGAL DISTORTION
SPECTRUM OF CH4 , Vincent Boudon, Jean Vander Auwera, Laurent Manceron, F. Kwabia Tchana, Tony GABARD, Badr
AMYAY, Mbaye Faye
TB07
11:05 – 11:20
HYDROGEN AND NITROGEN BROADENED ETHANE AND PROPANE ABSORPTION CROSS SECTIONS,
Robert J. Hargreaves, Dominique Appadoo, Brant E Billinghurst, Peter F. Bernath
9
TC. Mini-symposium: Spectroscopy in the Classroom
Chair: S. A. Cooke, Purchase College SUNY, Purchase, NY, USA
8:30 – 9:00
ar
y
TC01
INVITED TALK
PGOPHER IN THE CLASSROOM AND THE LABORATORY, Colin Western
TC02
9:05 – 9:20
SPECTROSCOPY FOR THE MASSES, Robert J. Le Roy, Scott Hopkins, William P. Power, Tong Leung, John Hepburn
TC03
9:22 – 9:37
RESEARCH AT A LIBERAL ARTS COLLEGE: MAKE SURE YOU HAVE A NET FOR YOUR HIGH WIRE ACT,
Mark D. Marshall, Helen O. Leung
TC04
9:39 – 9:54
A SPECTROSCOPY BASED P-CHEM LAB, INCLUDING A DETAILED TEXT AND LAB MANUAL, John Muenter
Intermission
in
TC05
HOW WE KNOW: SPECTROSCOPY IN THE FIRST YEAR AND BEYOND, Kristopher J Ooms
10:13 – 10:28
TC06
10:30 – 10:40
EXPANDED CHOICES FOR VIBRATION-ROTATION SPECTROSCOPY IN THE PHYSICAL CHEMISTRY TEACHING LABORATORY, Joel R Schmitz, David A Dolson
Pr
el
im
TC07
10:42 – 10:57
SPECTROSCOPIC CASE-BASED STUDIES IN A FLIPPED QUANTUM MECHANICS COURSE, Steven Shipman
TC08
THE H-ATOM SPECTRUM: NOT A CLASSROOM DEMONSTRATION . . . , Wolfgang Jäger
10:59 – 11:09
TC09
11:11 – 11:26
RAMAN INVESTIGATION OF TEMPERATURE PROFILES OF PHOSPHOLIPID DISPERSIONS IN THE BIOCHEMISTRY LABORATORY, Norman C. Craig
TC10
11:28 – 11:43
ONLINE AND CERTIFIABLE SPECTROSCOPY COURSES USING INFORMATION AND COMMUNICATION
TOOLS. A MODEL FOR CLASSROOMS AND BEYOND, Mangala Sunder Krishnan
10
TD. Conformers, isomers, chirality, stereochemistry
Chair: Emilio J. Cocinero, Universidad del Paı́s Vasco (UPV-EHU), Leioa, Spain
EXPERIMENTAL
STUDY
OF
THE
SiH2 OO
ISOMERIC
8:30 – 8:45
SYSTEM,
ar
y
TD01
A JOINT THEORETICAL AND
Michael C McCarthy, Jürgen Gauss
TD02
8:47 – 9:02
A MINTY MICROWAVE MENAGERIE: THE ROTATIONAL SPECTRA OF MENTHONE, MENTHOL, CARVACROL,
AND THYMOL, David Schmitz, V. Alvin Shubert, Thomas Betz, Barbara Michela Giuliano, Melanie Schnell
TD03
THE ROTATIONAL SPECTRUM AND
Ha Vinh Lam Nguyen, Wolfgang Stahl
CONFORMATIONAL
STRUCTURES
OF
METHYL
9:04 – 9:19
VALERATE,
in
TD04
9:21 – 9:36
ROTATIONAL SPECTRUM OF THE METHYL SALICYLATE-WATER COMPLEX: THE MISSING CONFORMER AND
THE TUNNELING MOTIONS, Supriya Ghosh, Javix Thomas, Yunjie Xu, Wolfgang Jäger
TD05
9:38 – 9:53
UNRAVELLING THE CONFORMATIONAL LANDSCAPE OF NICOTINOIDS: THE STRUCTURE OF COTININE BY
BROADBAND ROTATIONAL SPECTROSCOPY, Iciar Uriarte, Patricia Ecija, Emilio J. Cocinero, Cristobal Perez, Elena
Caballero-Mancebo, Alberto Lesarri
Pr
el
im
TD06
9:55 – 10:10
CONFORMATIONALLY RESOLVED STRUCTURES OF JET-COOLED PHENACETIN AND ITS HYDRATED CLUSTERS, Cheol Joo Moon, Ahreum Min, Ahreum Ahn, Myong Yong Choi
TD07
10:12 – 10:27
CONFORMATIONAL STRUCTURES OF JET-COOLED ACETAMINOPHEN-WATER CLUSTERS BY IR-DIP SPECTROSCOPY AND COMPUTATIONAL CALCULATIONS, Ahreum Min, Ahreum Ahn, Cheol Joo Moon, Myong Yong
Choi
Intermission
TD08
10:46 – 11:01
THE INHERENT CONFORMATIONAL PREFERENCES OF GLUTAMINE-CONTAINING PEPTIDES: THE ROLE FOR
SIDE-CHAIN BACKBONE HYDROGEN BONDS, Patrick S. Walsh, Carl McBurney, Samuel H. Gellman, Timothy S.
Zwier
TD09
11:03 – 11:18
APPLICATIONS OF STRUCTURAL MASS SPECTROMETRY TO METABOLOMICS: CLARIFYING BOND SPECIFIC
SPECTRAL SIGNATURES WITH ISOTOPE EDITED SPECTROSCOPY, Olga Gorlova, Conrad T. Wolke, Joseph Fournier,
Sean Colvin, Mark Johnson, Scott Miller
TD10
11:20 – 11:35
ALKALI METAL-GLUCOSE INTERACTION PROBED WITH INFRARED PRE-DISSOCIATION SPECTROSCOPY,
Steven J. Kregel, Brett Marsh, Jia Zhou, Etienne Garand
TD11
11:37 – 11:52
PROBING THE CONFORMATIONAL LANDSCAPE OF A POLYETHER BUILDING BLOCK BY RAMAN JET SPECTROSCOPY, Sebastian Bocklitz, Martin A. Suhm
TE. Instrument/Technique Demonstration
11
Chair: Ken Leopold, University of Minnesota, Minneapolis, MN, USA
ar
y
TE01
8:30 – 8:45
ELIMINATION OF THE VACUUM PUMP REQUIREMENT FOR HIGH-RESOLUTION ROTATIONAL SPECTROSCOPY., Jennifer Holt, Ryan W Daly, Christopher F. Neese, Frank C. De Lucia
TE02
8:47 – 8:57
3-D PRINTED SLIT NOZZLES FOR FOURIER TRANSFORM MICROWAVE SPECTROSCOPY, Chris Dewberry, Becca
Mackenzie, Susan Green, Ken Leopold
in
TE03
8:59 – 9:14
IMPLEMENTATION OF CMOS MILLIMETER-WAVE DEVICES FOR ROTATIONAL SPECTROSCOPY, Brian Drouin,
Adrian Tang, Erich T Schlecht, Adam M Daly, Emily Brageot, Qun Jane Gu, Yu Ye, Ran Shu, M.-C. Frank Chang, Rod M.
Kim
TE04
9:16 – 9:31
FAST SWEEPING DIRECT ABSORPTION (SUB)MILLIMETER SPECTROSCOPY BASED ON CHIRPED-PULSE
TECHNOLOGY, Brian Hays, Steven Shipman, Susanna L. Widicus Weaver
TE05
9:33 – 9:48
FAST SWEEPING DOUBLE RESONANCE MICROWAVE-(SUB)MILLIMETER SPECTROSCOPY BASED ON
CHIRPED PULSE TECHNOLOGY, Brian Hays, Susanna L. Widicus Weaver, Steven Shipman
Pr
el
im
Intermission
TE06
10:07 – 10:22
ON THE PHASE DEPENDENCE OF DOUBLE-RESONANCE EXPERIMENTS IN ROTATIONAL SPECTROSCOPY,
David Schmitz, V. Alvin Shubert, Anna Krin, David Patterson, Melanie Schnell
TE07
10:24 – 10:39
MICROWAVE THREE-WAVE MIXING EXPERIMENTS FOR CHIRALITY DETERMINATION: CURRENT STATUS,
Cristobal Perez, V. Alvin Shubert, David Schmitz, Chris Medcraft, Anna Krin, Melanie Schnell
TE08
10:41 – 10:56
A SEMI-AUTOMATED COMBINATION OF CHIRPED-PULSE AND CAVITY FOURIER TRANSFORM MICROWAVE
SPECTROSCOPY, Kyle N Crabtree, Marie-Aline Martin-Drumel, Michael C McCarthy, Sydney A Gaster, Taylor M Hall,
Deondre L Parks, Gordon G Brown
TE09
10:58 – 11:13
SUBMILLIMETER ABSORPTION SPECTROSCOPY IN SEMICONDUCTOR MANUFACTURING PLASMAS AND
COMPARISON TO THEORETICAL MODELS, Yaser H. Helal, Christopher F. Neese, Frank C. De Lucia, Paul R. Ewing,
Ankur Agarwal, Barry Craver, Phillip J. Stout, Michael D. Armacost
TE10
11:15 – 11:30
CLOUD COMPUTING FOR THE AUTOMATED ASSIGNMENT OF BROADBAND ROTATIONAL SPECTRA: PORTING AUTOFIT TO AMAZON EC2, Aaron C Olinger, Steven Shipman
12
TF. Mini-symposium: High-Precision Spectroscopy
Tuesday, June 23, 2015 – 1:30 PM
Chair: Trevor Sears, Brookhaven National Laboratory, Upton, NY, USA
1:30 – 2:00
ar
y
TF01
INVITED TALK
COMB-REFERENCED SUB-DOPPLER RESOLUTION INFRARED SPECTROMETER, Hiroyuki Sasada
TF02
2:05 – 2:20
SUB-DOPPLER RESOLUTION SPECTROSCOPY OF THE FUNDAMENTAL VIBRATION BAND OF HCl WITH A
COMB-REFERENCED SPECTROMETER, Kana Iwakuni, Hideyuki Sera, Masashi Abe, Hiroyuki Sasada
TF03
2:22 – 2:37
OBSERVATION AND ANALYSIS OF THE A1 -A2 SPLITTING OF CH3 D, Masashi Abe, Hideyuki Sera, Hiroyuki Sasada
TF04
2:39 – 2:54
HIGH RESOLUTION SPECTROSCOPY OF NAPHTHALENE CALIBRATED BY AN OPTICAL FREQUENCY COMB,
Akiko Nishiyama, Kazuki Nakashima, Ayumi Matsuba, Masatoshi Misono
in
TF05
2:56 – 3:11
OPTICAL FREQUENCY COMB FOURIER TRANSFORM SPECTROSCOPY WITH RESOLUTION EXCEEDING THE
LIMIT SET BY THE OPTICAL PATH DIFFERENCE, Aleksandra Foltynowicz, Lucile Rutkowski, Alexandra C Johanssson,
Amir Khodabakhsh, Piotr Maslowski, Grzegorz Kowzan, Kevin Lee, Martin Fermann
TF06
3:13 – 3:23
METROLOGY WITH AN OPTICAL FEEDBACK FREQUENCY STABILIZED CRDS, Samir Kassi, Johannes Burkart
Pr
el
im
Intermission
TF07
INVITED TALK
3:42 – 4:12
CAVITY ENHANCED ULTRAFAST TRANSIENT ABSORPTION SPECTROSCOPY, Thomas K Allison, Melanie Roberts
Reber, Yuning Chen
TF08
4:17 – 4:32
NOISE-IMMUNE CAVITY-ENHANCED OPTICAL FREQUENCY COMB SPECTROSCOPY, Lucile Rutkowski, Amir
Khodabakhsh, Alexandra C Johanssson, Aleksandra Foltynowicz
TF09
4:34 – 4:49
A NEW BROADBAND CAVITY ENHANCED FREQUENCY COMB SPECTROSCOPY TECHNIQUE USING GHz
VERNIER FILTERING., Jérôme Morville, Lucile Rutkowski, Georgi Dobrev, Patrick Crozet
TF10
4:51 – 5:06
A DECADE-SPANNING HIGH-RESOLUTION ASYNCHRONOUS OPTICAL SAMPLING BASED TERAHERTZ
TIME-DOMAIN SPECTROMETER, Jacob T Good, Daniel Holland, Ian A Finneran, Brandon Carroll, Marco A. Allodi,
Geoffrey Blake
TF11
5:08 – 5:23
DOPPLER-LIMITED SPECTROSCOPY WITH A DECADE-SPANNING TERAHERTZ FREQUENCY COMB,
Ian A Finneran, Jacob T Good, Daniel Holland, Brandon Carroll, Marco A. Allodi, Geoffrey Blake
TF12
5:25 – 5:40
DUAL COMB RAMAN SPECTROSCOPY ON CESIUM HYPERFINE TRANSITIONS-TOWARD A STIMULATE RAMAN SPECTRUM ON CF4 MOLECULE, Tze-Wei Liu, Yen-Chu Hsu, Wang-Yau Cheng
TG. Large amplitude motions, internal rotation
13
Chair: Kaori Kobayashi, University of Toyama, Toyama, Japan
ar
y
TG01
1:30 – 1:45
THE BAND OF CH3 CH2 D FROM 770-880 cm−1 , Adam M Daly, Brian Drouin, John Pearson, Peter Groner, Keeyoon
Sung, Linda Brown, Arlan Mantz, Mary Ann H. Smith
TG02
1:47 – 2:02
LOW-TEMPERATURE HIGH-RESOLUTION INFRARED SPECTRUM OF ETHANE-1D, C2 H5 D: ROTATIONAL
ANALYSIS OF THE ν17 BAND NEAR 805 cm−1 using ERHAM., Peter Groner, Adam M Daly, Brian Drouin, John Pearson,
Keeyoon Sung, Linda Brown, Arlan Mantz, Mary Ann H. Smith
TG03
2:04 – 2:19
MICROWAVE SPECTROSCOPY OF THE EXCITED VIBRATIONAL STATES OF METHANOL, John Pearson, Adam M
Daly
in
TG04
2:21 – 2:36
FIRST HIGH RESOLUTION ANALYSIS OF THE ν21 BAND OF PROPANE AT 921.4 cm−1 : EVIDENCE OF LARGEAMPLITUDE-MOTION TUNNELLING EFFECTS, Agnes Perrin, F. Kwabia Tchana, Jean-Marie Flaud, Laurent Manceron,
Jean Demaison, Natalja Vogt, Peter Groner, Walter Lafferty
Pr
el
im
TG05
2:38 – 2:53
TORSIONAL STRUCTURE IN THE Ã − X̃ SPECTRUM OF THE CH3 O2 AND CH2 XO2 RADICALS, Meng Huang,
Anne B McCoy, Terry A. Miller
TG06
2:55 – 3:10
UPDATE OF THE ANALYSIS OF THE PURE ROTATIONAL SPECTRUM OF EXCITED VIBRATIONS OF CH3 CH2 CN
, Adam M Daly, John Pearson, Shanshan Yu, Brian Drouin, Celina Bermúdez, José L. Alonso
Intermission
TG07
3:29 – 3:44
UNUSUAL INTERNAL ROTATION COUPLING IN THE MICROWAVE SPECTRUM OF PINACOLONE, YueYue Zhao,
Ha Vinh Lam Nguyen, Wolfgang Stahl, Jon T. Hougen
TG08
3:46 – 4:01
THE COMPLETE ROTATIONAL SPECTRUM OF CH3 NCO UP TO 376 GHz, Zbigniew Kisiel, Lucie Kolesniková, José
L. Alonso, Ivan Medvedev, Sarah Fortman, Manfred Winnewisser, Frank C. De Lucia
TG09
4:03 – 4:18
GAS PHASE CONFORMATIONS AND METHYL INTERNAL ROTATION FOR 2-PHENYLETHYL METHYL ETHER
AND ITS ARGON VAN DER WAALS COMPLEX FROM FOURIER TRANSFORM MICROWAVE SPECTROSCOPY,
Ranil M. Gurusinghe, Michael Tubergen
TG10
4:20 – 4:30
A COMPARISON OF BARRIER TO METHYL INTERNAL ROTATION OF METHYLSTYRENES: MICROWAVE SPECTROSCOPIC STUDY , Ranil M. Gurusinghe, Michael Tubergen
TG11
4:32 – 4:47
MICROWAVE SPECTRA AND AB INITIO STUDIES OF THE NE-ACETONE COMPLEX, Jiao Gao, Javix Thomas, Yunjie Xu, Wolfgang Jäger
TG12
4:49 – 5:04
THE EFFECTS OF INTERNAL ROTATION AND 14 N QUADRUPOLE COUPLING IN N-METHYLDIACETAMIDE,
Raphaela Kannengießer, Konrad Eibl, Ha Vinh Lam Nguyen, Wolfgang Stahl
TG13
5:06 – 5:21
A NEW HYBRID PROGRAM FOR FITTING ROTATIONALLY RESOLVED SPECTRA OF METHYLAMINE-LIKE
MOLECULES: APPLICATION TO 2-METHYLMALONALDEHYDE, Isabelle Kleiner, Jon T. Hougen
TG14
5:23 – 5:38
DETERMINATION OF TORSIONAL BARRIERS OF ITACONIC ACID AND N-ACETYLETHANOLAMINE USING
CHIRPED-PULSED FTMW SPECTROSCOPY, Josiah R Bailey, Timothy J McMahon, Ryan G Bird, David Pratt
14
TH. Radicals
Chair: Bernadette M. Broderick, University of Georgia, Athens, GA, USA
ar
y
TH01
1:30 – 1:45
AB INITIO SIMULATION OF THE PHOTOELECTRON SPECTRUM FOR METHOXY RADICAL, Lan Cheng, Marissa
L. Weichman, Jongjin B. Kim, Takatoshi Ichino, Daniel Neumark, John F. Stanton
TH02
1:47 – 2:02
JAHN-TELLER COUPLING IN THE METHOXY RADICAL: INSIGHTS INTO THE INFRARED SPECTRUM OF
MOLECULES WITH VIBRONIC COUPLING, Britta Johnson, Edwin Sibert
TH03
2:04 – 2:19
RE-EVALUATION OF HO3 STRUCTURE USING MILLIMETER-SUBMILLIMETER SPECTROSCOPY, Luyao Zou,
Brian Hays, Susanna L. Widicus Weaver
in
TH04
2:21 – 2:36
ON THE STARK EFFECT IN OPEN SHELL COMPLEXES EXHIBITING PARTIALLY QUENCHED ELECTRONIC
ANGULAR MOMENTUM, Gary E. Douberly, Christopher P. Moradi
TH05
2:38 – 2:53
INFRARED LASER SPECTROSCOPY AND AB INITIO COMPUTATIONS OF OH···(D2 O)N COMPLEXES IN HELIUM NANODROPLETS, Joseph T. Brice, Christopher M. Leavitt, Christopher P. Moradi, Gary E. Douberly, Federico J
Hernandez, Gustavo A Pino
Pr
el
im
TH06
2:55 – 3:10
VIBRATIONAL-TORSIONAL COUPLING REVEALED IN THE INFRARED SPECTRUM OF HE-SOLVATED nPROPYL RADICAL, Christopher P. Moradi, Bernadette M. Broderick, Jay Agarwal, Henry F. Schaefer III., Gary E. Douberly
TH07
3:12 – 3:27
VIBRONIC SPECTROSCOPY OF HETERO DIHALO-BENZYL RADICALS GENERATED BY CORONA DISCHARGE
: JET-COOLED CHLOROFLUOROBENZYL RADICALS, Young Yoon, Sang Lee
TH08
3:29 – 3:44
GROWING UP RADICAL: INVESTIGATION OF BENZYL-LIKE RADICALS WITH INCREASING CHAIN LENGTHS,
Joseph A. Korn, Khadija M. Jawad, Daniel M. Hewett, Timothy S. Zwier
Intermission
TH09
4:03 – 4:18
ANALYSIS OF ROTATIONALLY RESOLVED SPECTRA TO NON-DEGENERATE (a′′1 ) UPPER-STATE VIBRONIC
LEVELS IN THE Ã2 E ′′ − X̃ 2 A′2 ELECTRONIC TRANSITION OF NO3 , Mourad Roudjane, Terrance Joseph Codd, MingWei Chen, Henry Tran, Dmitry G. Melnik, Terry A. Miller, John F. Stanton
TH10
4:20 – 4:35
ANALYSIS OF ROTATIONALLY RESOLVED SPECTRA TO DEGENERATE (e′ ) UPPER-STATE VIBRONIC LEVELS
IN THE Ã2 E ′′ − X̃ 2 A′2 ELECTRONIC TRANSITION OF NO3 , Henry Tran, Terry A. Miller
TH11
4:37 – 4:52
ROVIBRONIC VARIATIONAL CALCULATIONS OF THE NITRATE RADICAL, Bryan Changala, Joshua H Baraban,
John F. Stanton
TH12
VIBRONIC STRUCTURE OF THE X̃ 2 A′2 STATE OF NO3 , Masaru Fukushima
4:54 – 5:09
TH13
5:11 – 5:26
HIGH-RESOLUTION LASER SPECTROSCOPY OF 14 NO3 RADICAL: VIBRATIONALLY EXCITED STATES OF THE
B 2 E ′ STATE, Kohei Tada, Shunji Kasahara, Takashi Ishiwata, Eizi Hirota
TH14
5:28 – 5:43
STRUCTURAL CHARACTERIZATION OF HYDROXYL RADICAL ADDUCTS IN AQUEOUS MEDIA, Ireneusz Janik,
G. N. R. Tripathi
TI. Dynamics/Kinetics/Ultrafast
15
Chair: Patrick Vaccaro, Yale University, New Haven, CT, USA
ar
y
TI01
1:30 – 1:45
MULTISCALE SPECTROSCOPY OF DIFFUSING MOLECULES IN CROWDED ENVIRONMENTS, Ahmed A Heikal
TI02
1:47 – 1:57
INVESTIGATING THE ROLE OF HUMAN SERUM ALBUMIN ON THE EXCITED STATE DYNAMICS OF INDOCYANINE GREEN USING SHAPED FEMTOSECOND LASER PULSES, Muath Nairat, Arkaprabha Konar, Marie Kaniecki,
Vadim V. Lozovoy, Marcos Dantus
TI03
1:59 – 2:14
ULTRAFAST SPECTROSCOPIC AND AB INITIO COMPUTATIONAL INVESTIGATIONS ON SOLVATION
DYNAMICS OF NEUTRAL AND DEPROTONATED TYROSINE., Takashige Fujiwara, Marek Z. Zgierski
in
TI04
2:16 – 2:31
WHICH ELECTRONIC AND STRUCTURAL FACTORS CONTROL THE PHOTOSTABILITY OF DNA AND RNA
PURINE NUCLEOBASES?, Marvin Pollum, Christian Reichardt, Carlos E. Crespo-Hernández, Lara Martı́nez-Fernández,
Inés Corral, Clemens Rauer, Sebastian Mai, Philipp Marquetand, Leticia González
TI05
2:33 – 2:48
ULTRAFAST DYNAMICS IN DNA AND RNA DERIVATIVES MONITORED BY BROADBAND TRANSIENT ABSORPTION SPECTRSCOPY, Matthew M Brister, Carlos E. Crespo-Hernández
Pr
el
im
TI06
2:50 – 3:05
CAN FEMTOSECOND TRANSIENT ABSORPTION SPECTROSCOPY PREDICT THE POTENTIAL OF SMALL
MOLECULES AS PERSPECTIVE DONORS FOR ORGANIC PHOTOVOLTAICS?, Regina DiScipio, Genevieve Sauve,
Carlos E. Crespo-Hernández
TI07
3:07 – 3:22
MOLECULE-LIKE CdSe NANOCLUSTERS PASSIVATED WITH STRONGLY INTERACTING LIGANDS: ENERGY
LEVEL ALIGNMENT AND PHOTOINDUCED ULTRAFAST CHARGE TRANSFER PROCESSES, Yizhou Xie, Meghan
B Teunis, Bill Pandit, Rajesh Sardar, Jinjun Liu
TI08
3:24 – 3:39
TOWARD THE ACCURATE SIMULATION OF TWO-DIMENSIONAL ELECTRONIC SPECTRA, Angelo Giussani, Artur Nenov, Javier Segarra-Martı́, Vishal K. Jaiswal, Ivan Rivalta, Elise Dumont, Shaul Mukamel, Marco Garavelli
Intermission
TI09
3:58 – 4:13
ULTRAFAST TERAHERTZ KERR EFFECT SPECTROSCOPY OF LIQUIDS AND BINARY MIXTURES,
Marco A. Allodi, Ian A Finneran, Geoffrey Blake
TI10
4:15 – 4:30
ULTRAFAST TERAHERTZ KERR EFFECT SPECTROSCOPY OF AROMATIC LIQUIDS, Ian A Finneran, Marco A. Allodi, Geoffrey Blake
TI11
4:32 – 4:47
VIBRATIONALLY-RESOLVED KINETIC ISOTOPE EFFECTS IN THE PROTON-TRANSFER DYNAMICS OF
GROUND-STATE TROPOLONE, Kathryn Chew, Zachary Vealey, Patrick Vaccaro
TI12
4:49 – 5:04
CHARACTERIZATION OF CHBrCl2 PHOTOLYSIS BY VELOCITY MAP IMAGING, W G Merrill, Amanda Case, Benjamin C. Haenni, Robert J. McMahon, Fleming Crim
TI13
5:06 – 5:21
REVERSIBILITY OF INTERSYSTEM CROSSING IN THE ã1 A1 (000) and ã1 A1 (010) STATES OF METHYLENE, CH2 ,
Anh T. Le, Trevor Sears, Gregory Hall
TI14
5:23 – 5:38
EFFICIENT SUPER ENERGY TRANSFER COLLISIONS THROUGH REACTIVE-COMPLEX FORMATION: H + SO2
, Jonathan M. Smith, Michael J. Wilhelm, Jianqiang Ma, HAI-LUNG Dai
TI15
5:40 – 5:55
FOURTH-ORDER VIBRATIONAL TRANSITION STATE THEORY AND CHEMICAL KINETICS, John F. Stanton,
Devin A. Matthews, Justin Z Gong
16
TJ. Rydberg Atoms and Molecules
Chair: Brian DeMarco, University of Illinois, Urbana, IL, USA
ar
y
TJ01
1:30 – 1:45
PRECISION SPECTROSCOPY IN COLD MOLECULES: THE FIRST ROTATIONAL INTERVALS OF He+
BY
HIGH2
RESOLUTION SPECTROSCOPY AND RYDBERG-SERIES EXTRAPOLATION, Paul Jansen, Luca Semeria, Simon
Scheidegger, Frederic Merkt
TJ02
1:47 – 2:02
MICROWAVE SPECTROSCOPY OF THE CALCIUM 4snf → 4s(n+1)d, 4sng, 4snh, 4sni, AND 4snk TRANSITIONS,
Jirakan Nunkaew, Tom Gallagher
TJ03
2:04 – 2:14
PHASE DEPENDENCE IN ABOVE THRESHOLD IONIZATION IN THE PRESENCE OF A MICROWAVE FIELD,
Vincent Carrat, Eric Magnuson, Tom Gallagher
in
TJ04
2:16 – 2:26
MICROWAVE TRANSITIONS BETWEEN PAIR STATES COMPOSED OF TWO Rb RYDBERG ATOMS, Jeonghun Lee,
Tom Gallagher
TJ05
HIGH-RESOLUTION SPECTROSCOPY OF LONG-RANGE MOLECULAR STATES OF
Edward E. Eyler, Yoann Bruneau, Phillip Gould, W.C. Stwalley
85
2:28 – 2:43
Rb2 , Ryan Carollo,
Pr
el
im
TJ06
2:45 – 3:00
DOUBLE RESONANCE SPECTROSCOPY OF BaF AUTOIONIZING RYDBERG STATES, Timothy J Barnum, David
Grimes, Yan Zhou, Robert W Field
TJ07
3:02 – 3:17
MILLIMETER WAVE SPECTROSCOPY OF RYDBERG STATES OF MOLECULES IN THE REGION OF 260-295 GHz,
David Grimes, Yan Zhou, Timothy J Barnum, Robert W Field
Intermission
TJ08
3:36 – 3:51
EFFECTIVE ION-IN-MOLECULE POTENTIALS FOR NON-PENETRATING RYDBERG STATES OF POLAR
MOLECULES, Stephen Coy, David Grimes, Yan Zhou, Robert W Field, Bryan M. Wong
TJ09
3:53 – 4:08
ELECTRONIC STRUCTURE OF THE X 1 Σ+ ION CORE OF CaF RYDBERG STATES, Stephen Coy, Joshua H Baraban,
David Grimes, Timothy J Barnum, Robert W Field, Bryan M. Wong
TJ10
4:10 – 4:25
SYSTEMATICS OF RYDBERG SERIES OF DIATOMIC MOLECULES AND CORRELATION DIAGRAMS,
Chun-Woo Lee
TJ11
INVITED TALK
4:27 – 4:42
OBSERVATION OF CS TRILOBITE MOLECULES WITH KILO-DEBYE MOLECULAR FRAME PERMANENT ELECTRIC DIPOLE MOMENTS, James P Shaffer
TJ12
4:44 – 4:59
MOLECULE FORMATION AND STATE-CHANGING COLLISIONS OF SINGLE RYDBERG ATOMS IN A BEC,
Kathrin Sophie Kleinbach, Michael Schlagmüller, Tara Cubel Liebisch, Karl Magnus Westphal, Fabian Böttcher, Robert
Löw, Sebastian Hofferberth, Tilman Pfau, Jesús Pérez-Rı́os, C. H. Greene
TJ13
5:01 – 5:16
RYDBERG, VALENCE AND ION-PAIR QUINTET STATES OF O2 , Gabriel J. Vazquez, Hans P. Liebermann, H. LefebvreBrion
TJ14
5:18 – 5:33
AB INITIO STUDY OF THE H, J, I, I′ AND I′′ 3 Πu SUPEREXCITED STATES OF O2 , Gabriel J. Vazquez, Hans P. Liebermann, H. Lefebvre-Brion
17
WA. Plenary
Wednesday, June 24, 2015 – 8:30 AM
Chair: Leslie Looney, University of Illinois, Urbana, IL, USA
8:30
ar
y
RAO AWARDS
Presentation of Awards by Yunjie Xu, University of Alberta
2014 Rao Award Winners
Grant Buckingham, University of Colorado
Kathryn Chew, Yale University
Yu-Hsuan Huang, National Chiao Tung University
in
MILLER PRIZE
Introduction by Mike Heaven, Emory University
8:40
WA01
8:45 – 9:00
INFRARED LASER STARK SPECTROSCOPY OF THE OH···CH3 OH COMPLEX ISOLATED IN SUPERFLUID HELIUM DROPLETS, Christopher M. Leavitt, Joseph T. Brice, Gary E. Douberly, Federico J Hernandez, Gustavo A Pino
Pr
el
im
FLYGARE AWARDS
Introduction by Trevor Sears, Brookhaven National Laboratory
9:05
WA02
9:10 – 9:25
WHAT CAN WE EXPECT OF HIGH-RESOLUTION SPECTROSCOPIES ON CARBOHYDRATES?, Emilio J. Cocinero,
Patricia Ecija, Iciar Uriarte, Imanol Usabiaga, José A. Fernández, Francisco J. Basterretxea, Alberto Lesarri, Benjamin G.
Davis
WA03
9:30 – 9:45
CONSTRUCTION OF POTENTIAL ENERGY SURFACES FOR THEORETICAL STUDIES OF SPECTROSCOPY AND
DYNAMICS, Richard Dawes
Intermission
WA04
10:35 – 10:50
MILLIMETER AND SUBMILLIMETER STUDIES OF O(1 D) INSERTION REACTIONS TO FORM MOLECULES OF
ASTROPHYSICAL INTEREST, Brian Hays, Nadine Wehres, Bridget Alligood Deprince, Althea A. M. Roy, Jacob Laas,
Susanna L. Widicus Weaver
WA05
10:55 – 11:10
TERAHERTZ AND INFRARED LABORATORY SPECTROSCOPY IN SUPPORT OF NASA MISSIONS, Shanshan Yu
COBLENTZ AWARD
Presentation of Award by Mark Druy, Coblentz Society
11:15
WA06
Coblentz Society Award Lecture
11:20 – 12:00
LASER SPECTROSCOPY OF RADICALS, CARBENES, AND IONS IN SUPERFLUID HELIUM DROPLETS,
Gary E. Douberly
18
WF. Mini-symposium: High-Precision Spectroscopy
Wednesday, June 24, 2015 – 1:30 PM
Chair: Kevin Cossel, JILA - University of Colorado, Boulder, CO, USA
ar
y
WF01
INVITED TALK
1:30 – 2:00
ULTRASENSITIVE, HIGH ACCURACY MEASUREMENTS OF TRACE GAS SPECIES, David A. Long, Adam J.
Fleisher, David F. Plusquellic, Joseph Hodges
WF02
2:05 – 2:20
PROBING BUFFER-GAS COOLED MOLECULES WITH DIRECT FREQUENCY COMB SPECTROSCOPY IN THE
MID-INFRRARED, Ben Spaun, Bryan Changala, Bryce J Bjork, Oliver H Heckl, David Patterson, John M. Doyle, Jun Ye
WF03
2:22 – 2:37
FREQUENCY-AGILE DIFFERENTIAL CAVITY RING-DOWN SPECTROSCOPY, Zachary Reed, Joseph Hodges
in
WF04
2:39 – 2:54
QUANTUM-NOISE-LIMITED CAVITY RING-DOWN SPECTROSCOPY IN THE MID-INFRARED, Adam J. Fleisher,
David A. Long, Qingnan Liu, Joseph Hodges
WF05
2:56 – 3:11
MOLECULAR LINE PARAMETERS PRECISELY DETERMINED BY A CAVITY RING-DOWN SPECTROMETER,
Shui-Ming Hu, Yan Tan, Jin Wang, Yan Lu, Cunfeng Cheng, Yu Robert Sun, An-Wen Liu
Pr
el
im
WF06
3:13 – 3:23
BROADBAND COMB-RESOLVED CAVITY ENHANCED SPECTROMETER WITH GRAPHENE MODULATOR,
Kevin Lee, Christian Mohr, Jie Jiang, Martin Fermann, Chien-Chung Lee, Thomas R Schibli, Grzegorz Kowzan, Piotr
Maslowski
Intermission
WF07
INVITED TALK
3:42 – 4:12
DUAL-COMB SPECTROSCOPY IN THE OPEN AIR, Greg B Rieker, Andrew Klose, Scott Diddams, Ian Coddington,
Fabrizio Giorgetta, Laura Sinclair, Esther Baumann, Gar-Wing Truong, Gabriel Ycas, William C Swann, Nathan R. Newbury
WF08
4:17 – 4:32
FREQUENCY-COMB REFERENCED SPECTROSCOPY OF ν4 AND ν5 HOT BANDS IN THE ν1 +ν3 COMBINATION
BAND OF C2 H2 , Sylvestre Twagirayezu, Matthew Cich, Trevor Sears, C. McRaven, Gregory Hall
WF09
4:34 – 4:49
LOCAL PERTURBATIONS IN THE (10110) AND (10101) LEVELS OF C2 H2 FROM FREQUENCY COMBREFERENCED SPECTROSCOPY, Trevor Sears, Sylvestre Twagirayezu, Damien Forthomme, Gregory Hall, Matthew Cich
WF10
4:51 – 5:06
NOISE-IMMUNE CAVITY-ENHANCED OPTICAL HETERODYNE MOLECULAR SPECTROMETRY MODELLING
UNDER SATURATED ABSORPTION, Patrick Dupré
WF11
5:08 – 5:23
MAGNETIC SPIN-TORSION COUPLING IN METHANOL, L. H. Coudert, C. Gutle, T. R. Huet, Jens-Uwe Grabow
WF12
5:25 – 5:40
SPIN-ROTATION HYPERFINE SPLITTINGS AT MODERATE TO HIGH J VALUES IN METHANOL, Li-Hong Xu, Jon
T. Hougen, Sergey Belov, G Yu GOLUBIATNIKOV, Alexander Lapinov, V. Ilyushin, E. A. Alekseev, A. A. Mescheryakov
WG. Mini-symposium: Accelerator-Based Spectroscopy
19
Chair: J. Oomens, Radboud University, Nijmegen, The Netherlands
ar
y
WG01
INVITED TALK
1:30 – 2:00
IR SPECTROSCOPY ON PEPTIDES AND PROTEINS AFTER ION MOBILITY SELECTION AND IN LIQUID HELIUM
DROPLETS , Gert von Helden
WG02
2:05 – 2:20
COMBINING THE POWER OF IRMPD WITH ION-MOLECULE REACTIONS: THE STRUCTURE AND REACTIVITY
OF RADICAL IONS OF CYSTEINE AND ITS DERIVATIVES, Michael Lesslie, Sandra Osburn, Giel Berden, J. Oomens,
Victor Ryzhov
WG03
2:22 – 2:37
FAR-IR ACTION SPECTROSCOPY OF AMINOPHENOL AND ETHYLVANILLIN: EXPERIMENT AND THEORY,
Vasyl Yatsyna, Raimund Feifel, Vitali Zhaunerchyk, Daniël Bakker, Anouk Rijs
in
WG04
2:39 – 2:54
OPPORTUNITIES FOR GAS-PHAS MOLECULAR SPECTROSCOPY ON THE VLS-PGM BEAMLINE AT THE CANADIAN LIGHT SOURCE, Michael A MacDonald
WG05
THERMAL DECOMPOSITION OF C7 H7 RADICALS; BENZYL,
Grant Buckingham, Barney Ellison, John W Daily, Musahid Ahmed
TROPYL,
AND
2:56 – 3:11
NORBORNADIENYL,
Pr
el
im
Intermission
WG06
3:30 – 3:40
NONDIPOLE EFFECTS IN CHIRAL SYSTEMS MEASURED WITH LINEARLY POLARIZED LIGHT, K P Bowen, O
Hemmers, R Guillemin, W C Stolte, M N Piancastelli, D W Lindle
WG07
3:42 – 3:57
APPLICATIONS OF THE VUV FOURIER TRANSFORM SPECTROMETER AT SYNCHROTRON SOLEIL ,
Nelson de Oliveira, Denis Joyeux, Kenji Ito, Berenger Gans, Laurent Nahon
WG08
3:59 – 4:14
FORBIDDEN TRANSITIONS IN THE VUV SPECTRUM OF N2 , Alan Heays, Ming Li Niu, Nelson de Oliveira, Edcel
John Salumbides, Brenton R Lewis, Wim Ubachs, Ewine van Dishoeck
WG09
4:16 – 4:31
SYNCHROTRON INFRARED SPECTROSCOPY OF ν4 , ν10 , ν11 AND ν14 STATES OF THIIRANE, Corey Evans, Jason
P Carter, Don McNaughton, Andy Wong, Dominique Appadoo
WG10
4:33 – 4:48
FINGERPRINTS OF INTRAMOLECULAR HYDROGEN BONDS: SYNCHROTRON-BASED FAR IR STUDY OF THE
CIS AND TRANS CONFORMERS OF 2-FLUOROPHENOL, Aimee Bell, James Singer, Jennifer van Wijngaarden
WG11
4:50 – 5:05
INFRARED CROSS-SECTIONS OF NITRO-DERIVATIVE VAPORS: NEW SPECTROSCOPIC SIGNATURES OF EXPLOSIVE TAGGANTS AND DEGRADATION PRODUCTS , Arnaud Cuisset, Gaël Mouret, Olivier Pirali, Sébastien Gruet,
Gérard Pascal Piau, Gilles Fournier
WG12
5:07 – 5:22
CHARACTERIZATION OF REACTION PATHWAYS IN LOW TEMPERATURE OXIDATION OF TETRAHYDROFURAN WITH MULTIPLEXED PHOTOIONIZATION MASS SPECTROMETRY TECHNIQUE, Ivan Antonov, Leonid
Sheps
20
WH. Clusters/Complexes
Chair: Elangannan Arunan, Indian Institute of Science, Bangalore, India
ar
y
WH01
1:30 – 1:45
A STRANGE COMBINATION BAND OF THE CROSS-SHAPED COMPLEX CO2 -CS2 , Nasser Moazzen-Ahmadi,
Bob McKellar
WH02
1:47 – 2:02
RE-ANALYSIS OF THE DISPERSED FLUORESCENCE SPECTRA OF THE C3 -RARE GAS ATOM COMPLEXES, YiJen Wang, Anthony Merer, Yen-Chu Hsu
WH03
INFARED SPECTROSCOPY OF Mn(CO2 )−
n CLUSTER ANIONS, Michael C Thompson, J. Mathias Weber
2:04 – 2:19
WH04
2:21 – 2:36
−
INFRARED SPECTROSCOPY OF (N2 O)−
n AND (N2 O)m O CLUSTER ANIONS, Michael C Thompson, J. Mathias Weber
in
WH05
2:38 – 2:53
INFRARED SPECTROSCOPY OF PHENOL+ -TRIETHYLSILANE DIHYDROGEN-BONDED CLUSTER: INTRINSIC
STRENGTH OF THE Si-H· · · H-O DYHYDROGEN BOND, Haruki Ishikawa, Takayuki Kawasaki, Risa Inomata
WH06
2:55 – 3:10
INFRARED SPECTROSCOPY OF HYDROGEN-BONDED CLUSTERS OF PROTONATED HISTIDINE, Makoto Kondo,
Yasutoshi Kasahara, Haruki Ishikawa
Pr
el
im
WH07
3:12 – 3:27
THEORETICAL INVESTIGATION OF THE UV/VIS PHOTODISSOCIATION DYNAMICS OF ICN− (Ar)n and
BrCN− (Ar)n , Bernice Opoku-Agyeman, Anne B McCoy
WH08
3:29 – 3:44
DISPERSION-DOMINATED π -STACKED COMPLEXES CONSTRUCTED ON A DYNAMIC SCAFFOLD,
Deacon Nemchick, Michael Cohen, Patrick Vaccaro
Intermission
WH09
4:03 – 4:18
THE COMPETITION BETWEEN INSERTION AND SURFACE BINDING OF BENZENE TO THE WATER HEPTAMER,
Patrick S. Walsh, Daniel P. Tabor, Edwin Sibert, Timothy S. Zwier
WH10
4:20 – 4:35
VIBRATIONAL SPECTROSCOPY OF BENZENE-(WATER)N CLUSTERS WITH N = 6, 7, Daniel P. Tabor, Edwin Sibert, Ryoji Kusaka, Patrick S. Walsh, Timothy S. Zwier
WH11
4:37 – 4:52
THEORETICAL STUDY OF THE IR SPECTROSCOPY OF BENZENE-(WATER)N CLUSTERS, Daniel P. Tabor, Edwin
Sibert, Ryoji Kusaka, Patrick S. Walsh, Timothy S. Zwier
WH12
4:54 – 5:09
SPECTROSCOPIC INVESTIGATION OF TEMPERATURE EFFECTS ON THE HYDRATION STRUCTURE OF THE
PHENOL CLUSTER CATION, Reona Yagi, Yasutoshi Kasahara, Haruki Ishikawa
WH13
5:11 – 5:26
ULTRAVIORET AND INFRARED PHOTODISSOCIATION SPECTROSCOPY OF HYDRATED ANILINIUM ION,
Itaru Kurusu, Reona Yagi, Yasutoshi Kasahara, Haruki Ishikawa
WH14
5:28 – 5:43
WATER-NETWORK MEDIATED, ELECTRON INDUCED PROTON TRANSFER IN ANIONIC [C5 H5 N·(H2 O)n ]−
CLUSTERS: SIZE DEPENDENT FORMATION OF THE PYRIDINIUM RADICAL FOR n ≥ 3, Andrew F DeBlase, Gary
H Weddle, Kaye A Archer, Kenneth D. Jordan, Mark Johnson
21
WI. Astronomy
Chair: Holger S. P. Müller, Universität zu Köln, Köln, NRW, Germany
ar
y
WI01
1:30 – 1:45
THE NEW ALMA PROTOTYPE 12 M TELSCOPE OF THE ARIZONA RADIO OBSERVATORY: TRANSPORT,
RECOMMISSIONING, AND FIRST LIGHT, Lucy Ziurys, N J Emerson, T W Folkers, R W Freund, D Forbes, G P Reiland,
M McColl, S C Keel, S H Warner, J Kingsley, DeWayne T Halfen
WI02
1:47 – 2:02
FIRST SCIENTIFIC OBSERVATIONS WITH THE NEW ALMA PROTOTYPE ANTENNA OF THE ARIZONA RADIO
OBSERVATORY: HCN AND CCH IN THE HELIX NEBULA, Lucy Ziurys, Deborah Schmidt
WI03
CCH AND HNC IN PLANETARY NEBULAE, Deborah Schmidt, Lucy Ziurys
2:04 – 2:19
in
WI04
2:21 – 2:36
MAPPING THE SPATIAL DISTRIBUTION OF METAL-BEARING OXIDES IN VY CANIS MAJORIS,
Andrew Burkhardt, S. Tom Booth, Anthony Remijan, Brandon Carroll, Lucy Ziurys
WI05
2:38 – 2:53
C+ AND THE CONNECTION BETWEEN DIFFERENT TRACERS OF THE DIFFUSE INTERSTELLAR MEDIUM,
Steven Federman, Johnathan S Rice, Jorge L Pineda, William D Langer, Paul F Goldsmith, Nicolas Flagey
Pr
el
im
WI06
2:55 – 3:10
INFERRING THE TEMPERATURE AND DENSITY OF DIFFUSE INTERSTELLAR CLOUDS FROM C3 OBSERVATIONS, Nicole Koeppen, Benjamin J. McCall
WI07
3:12 – 3:27
NEW BACKGROUND INFRARED SOURCES FOR STUDYING THE GALACTIC CENTER’S INTERSTELLAR GAS ,
Thomas R. Geballe, Takeshi Oka, E. Lambrides, S. C. C. Yeh, B. Schlegelmilch, Miwa Goto, C W Westrick
WI08
3:29 – 3:44
CO SPECTRAL LINE ENERGY DISTRIBUTIONS IN ORION SOURCES: TEMPLATES FOR EXTRAGALACTIC OBSERVATIONS, Nick Indriolo, Edwin Bergin
Intermission
WI09
4:03 – 4:18
THE DISTRIBUTION, EXCITATION, AND ABUNDANCE OF C+ , CH+ , AND CH IN ORION KL, Harshal Gupta, Patrick
Morris, Zsofia Nagy, John Pearson, Volker Ossenkopf
WI10
4:20 – 4:35
THE DISTRIBUTION OF SH+ AROUND ORION KL , Harshal Gupta, Karl M. Menten, Zsofia Nagy, Patrick Morris,
Volker Ossenkopf, Nathan Crockett, John Pearson
WI11
4:37 – 4:52
CARMA 1 CM LINE SURVEY OF ORION-KL, Douglas Friedel, Leslie Looney, Joanna F. Corby, Anthony Remijan
WI12
4:54 – 5:09
CHEMICAL COMPLEXITY IN THE SHOCKED OUTFLOW L1157-B REVEALED BY CARMA, Niklaus M Dollhopf,
Brett A. McGuire, Brandon Carroll, Anthony Remijan
WI13
5:11 – 5:26
THE CURIOUS CASE OF NH2 OH: HUNTING A DIRECT AMINO ACID PRECURSOR SPECIES IN THE INTERSTELLAR MEDIUM, Brett A. McGuire, Brandon Carroll, Niklaus M Dollhopf, Nathan Crockett, Geoffrey Blake, Anthony
Remijan
WI14
5:28 – 5:43
NEW RESULTS FROM THE CARMA LARGE-AREA STAR FORMATION SURVEY (CLASSY) , Robert J Harris, Leslie
Looney, Dominique M. Segura-Cox, Manuel Fernandez-Lopez, Lee Mundy, Shaye Storm, Maxime Rizzo, Katherine Lee,
Héctor Arce
WI15
5:45 – 6:00
ADMIT: ALMA DATA MINING TOOLKIT, Douglas Friedel, Leslie Looney, Lisa Xu, Marc W. Pound, Peter J. Teuben,
Kevin P. Rauch, Lee Mundy, Jeffrey S. Kern
22
WJ. Non-covalent interactions
Chair: Wolfgang Jäger, University of Alberta, Edmonton, AB, Canada
ar
y
WJ01
1:30 – 1:45
FORMATION OF COMPLEXES c-C3 H6 ···MCl (M = Ag or Cu) AND THEIR CHARACTERIZATION BY BROADBAND
ROTATIONAL SPECTROSCOPY, Daniel P. Zaleski, John Connor Mullaney, Nick Walker, Anthony Legon
WJ02
1:47 – 2:02
ROTATIONAL SPECTROSCOPY OF MONOFLUOROETHANOL AGGREGATES WITH ITSELF AND WITH WATER,
Javix Thomas, Wenyuan Huang, Xunchen Liu, Wolfgang Jäger, Yunjie Xu
WJ03
2:04 – 2:19
O-TOLUIC ACID MONOMER AND MONOHYDRATE: ROTATIONAL SPECTRA, STRUCTURES, AND ATMOSPHERIC IMPLICATIONS, Elijah G Schnitzler, Brandi L M Zenchyzen, Wolfgang Jäger
in
WJ04
2:21 – 2:36
A ROVIBRATIONAL ANALYSIS OF THE WATER BENDING VIBRATION IN OC-H2 O AND A MORPHED POTENTIAL OF THE COMPLEX, Luis A. Rivera-Rivera, Sean D. Springer, Blake A. McElmurry, Igor I Leonov, Robert R. Lucchese, John W. Bevan, L. H. Coudert
WJ05
2:38 – 2:53
THE MICROWAVE SPECTRUM AND UNEXPECTED STRUCTURE OF THE BIMOLECULAR COMPLEX FORMED
BETWEEN ACETYLENE AND (Z)-1-CHLORO-2-FLUOROETHYLENE, Nazir D. Khan, Helen O. Leung, Mark D. Marshall
Pr
el
im
WJ06
2:55 – 3:10
CHLORINE NUCLEAR QUADRUPOLE HYPERFINE STRUCTURE IN THE VINYL CHLORIDE–HYDROGEN CHLORIDE COMPLEX, Helen O. Leung, Mark D. Marshall, Joseph P. Messinger
WJ07
3:12 – 3:27
ELECTRONIC COMMUNICATION IN COVALENTLY vs. NON-COVALENTLY BONDED POLYFLUORENE SYSTEMS: THE ROLE OF THE COVALENT LINKER., Brandon Uhler, Neil J Reilly, Marat R Talipov, Maxim Ivanov, Qadir
Timerghazin, Rajendra Rathore, Scott Reid
Intermission
WJ08
3:46 – 4:01
A GENERAL TRANSFORMATION TO CANONICAL FORM FOR POTENTIALS IN PAIRWISE INTERMOLECULAR
INTERACTIONS, Jay R. Walton, Luis A. Rivera-Rivera, Robert R. Lucchese, John W. Bevan
WJ09
4:03 – 4:18
THREE-DIMENSIONAL WATER NETWORKS SOLVATING AN EXCESS POSITIVE CHARGE: NEW INSIGHTS INTO
THE MOLECULAR PHYSICS OF ION HYDRATION, Conrad T. Wolke, Joseph Fournier, Gary H Weddle, Evangelos
Miliordos, Sotiris Xantheas, Mark Johnson
WJ10
4:20 – 4:35
MATRIX ISOLATION INFRARED SPECTROSCOPY OF A SERIES OF 1:1 PHENOL-WATER COMPLEXES ,
Pujarini Banerjee, Tapas Chakraborty
WJ11
4:37 – 4:52
MATRIX ISOLATION IR SPECTROSCOPY AND QUANTUM CHEMISTRY STUDY OF 1:1 Π-HYDROGEN BONDED
COMPLEXES OF BENZENE WITH A SERIES OF FLUOROPHENOLS, Pujarini Banerjee, Tapas Chakraborty
WJ12
4:54 – 5:09
MATRIX ISOLATION IR SPECTROSCOPY OF 1:1 COMPLEXES OF ACETIC ACID AND TRIHALOACETIC ACIDS
WITH WATER AND BENZENE, Pujarini Banerjee, Tapas Chakraborty
WJ13
5:11 – 5:21
SPECTROSCOPIC INVESTIGATION OF THE EFFECTS OF ENVIRONMENT ON NEWLY-DEVELOPED NEAR INFRARED EMITTING DYES, Louis E. McNamara, Nalaka Liyanage, Jared Delcamp, Nathan I Hammer
WJ14
5:23 – 5:38
SPECTROSCOPIC SIGNATURES AND STRUCTURAL MOTIFS IN ISOLATED AND HYDRATED XANTHINE AND
ITS METHYLATED DERIVATIVES, Vipin Bahadur Singh
RA. Metal containing
23
Thursday, June 25, 2015 – 8:30 AM
Chair: Damian L Kokkin, Arizona State University, Tempe, Arizona, USA
ar
y
RA01
8:30 – 8:45
HYPERFINE RESOLVED PURE ROTATIONAL SPECTROSCOPY OF ScN, YN, AND BaNH (X1 Σ+ ): INSIGHT INTO
METAL-NITROGEN BONDING, Lindsay N. Zack, Matthew Bucchino, Justin Young, Marshall Binns, Phillip M. Sheridan,
Lucy Ziurys
RA02
8:47 – 9:02
THE SUBMILLIMETER/THz SPECTRUM OF AlH (X1 Σ+ ), CrH (X6 Σ+ ), and SH+ (X3 Σ− ), DeWayne T Halfen, Lucy
Ziurys
RA03
9:04 – 9:19
FORMATION OF M-C≡C-Cl (M = Ag or Cu) AND CHARACTERIZATION BY ROTATIONAL SPECTROSCOPY,
Daniel P. Zaleski, David Peter Tew, Nick Walker, Anthony Legon
in
RA04
9:21 – 9:36
(CH3 )3 N···AgI AND H3 N···AgI STUDIED BY BROADBAND ROTATIONAL SPECTROSCOPY AND AB INITIO CALCULATIONS, Dror M. Bittner, Daniel P. Zaleski, Susanna L. Stephens, Nick Walker, Anthony Legon
RA05
9:38 – 9:53
MICROWAVE SPECTRA AND GEOMETRIES OF C2 H2 · · · AgI and C2 H4 · · · AgI, Susanna L. Stephens, David Peter Tew,
Nick Walker, Anthony Legon
Pr
el
im
Intermission
RA06
10:12 – 10:27
EVALUATION OF THE EXOTHERMICITY OF THE CHEMI-IONIZATION REACTION Sm + O → SmO+ + e− , Richard
M Cox, JungSoo Kim, Peter Armentrout, Joshua Bartlett, Robert A. VanGundy, Michael Heaven, Joshua J. Melko, Shaun
Ard, Nicholas S. Shuman, Albert Viggiano
RA07
10:29 – 10:44
The PERMANENT ELECTRIC DIPOLE MOMENT AND HYPERFINE INTERACTION IN GOLD SULFIDE, AuS ,
Ruohan Zhang, Damian L Kokkin, Thomas D. Varberg, Timothy Steimle
RA08
10:46 – 11:01
HIGH-ACCURACY CALCULATION OF Cu ELECTRIC-FIELD GRADIENTS: A REVISION OF THE Cu NUCLEAR
QUADRUPOLE MOMENT VALUE , Lan Cheng, Devin A. Matthews, Jürgen Gauss, John F. Stanton
RA09
11:03 – 11:18
CATION-π AND CH-π INTERACTIONS IN THE COORDINATION AND SOLVATION OF Cu+ (ACETYLENE)n
(n=1-6) COMPLEXES INVESTIGATED VIA INFRARED PHOTODISSOCIATION SPECTROSCOPY ,
Antonio David Brathwaite, Richard S. Walters, TIMOTHY B WARD, Michael A Duncan
RA10
11:20 – 11:35
ANION PHOTOELECTRON SPECTROSCOPIC STUDIES OF NbCr(CO)−
n (n = 2,3) HETEROBIMETALLIC CARBONYL COMPLEXES, Melissa A. Baudhuin, Praveenkumar Boopalachandran, Doreen Leopold
RA11
11:37 – 11:52
MASS-ANALYZED THRESHOLD IONIZATION SPECTROSCOPY OF CYCLIC La(C5 H6 ) FORMED BY La ATOM
ACTIVATION OF PENTYNE AND PENTADIENE, Wenjin Cao, Yuchen Zhang, Dong-Sheng Yang
24
RB. Mini-symposium: Accelerator-Based Spectroscopy
Chair: Gert von Helden, Fritz Haber Institute - MPG, Berlin, Germany
ar
y
RB01
INVITED TALK
8:30 – 9:00
PROBING INTRA- AND INTER- MOLECULAR INTERACTIONS VIA IRMPD EXPERIMENTS AND COMPUTATIONAL CHEMISTRY, Scott Hopkins, Terry McMahon
RB02
9:05 – 9:20
EXPLORING CONFORMATION SELECTIVE FAR INFRARED ACTION SPECTROSCOPY OF ISOLATED
MOLECULES AND SOLVATED CLUSTERS, Daniël Bakker, Anouk Rijs, Jérôme Mahé, Marie-Pierre Gaigeot
RB03
9:22 – 9:37
FIRST INFRARED PREDISSOCIATION SPECTRA OF He-TAGGED PROTONATED PRIMARY ALCOHOLS AT 4
K, Alexander Stoffels, Britta Redlich, J. Oomens, Oskar Asvany, Sandra Brünken, Pavol Jusko, Sven Thorwirth, Stephan
Schlemmer
in
RB04
9:39 – 9:49
METAL ION INDUCED PAIRING OF CYTOSINE BASES: FORMATION OF I-MOTIF STRUCTURES IDENTIFIED BY
IR ION SPECTROSCOPY, Juehan Gao, Giel Berden, J. Oomens
RB05
9:51 – 10:06
MOLECULAR PROPERTIES OF THE ”ANTI-AROMATIC” SPECIES CYCLOPENTADIENONE, C5 H5 =0, Thomas Ormond, Barney Ellison, John W Daily, John F. Stanton, Musahid Ahmed, Timothy S. Zwier, Patrick Hemberger
Pr
el
im
Intermission
RB06
10:25 – 10:40
HIGH-RESOLUTION SYNCHROTRON INFRARED SPECTROSCOPY OF THIOPHOSGENE: THE ν1 , ν5 , 2ν4 , and ν2
+ 2ν6 bands , Bob McKellar, Brant E Billinghurst
RB07
10:42 – 10:57
THE SOLEIL VIEW ON SULFUR OXIDES: THE S2 O BENDING MODE ν2 AT 380 cm−1 AND ITS ANALYSIS USING
AN AUTOMATED SPECTRAL ASSIGNMENT PROCEDURE (ASAP), Marie-Aline Martin-Drumel, Christian Endres,
Oliver Zingsheim, T. Salomon, Jennifer van Wijngaarden, Olivier Pirali, Sébastien Gruet, Frank Lewen, Stephan Schlemmer,
Michael C McCarthy, Sven Thorwirth
RB08
10:59 – 11:14
THE SOLEIL VIEW ON SULFUR RICH OXIDES: THE ν3 MODE OF S2 O REVISITED, Sven Thorwirth, Marie-Aline
Martin-Drumel, Christian Endres, Oliver Zingsheim, T. Salomon, Jennifer van Wijngaarden, Olivier Pirali, Sébastien Gruet,
Frank Lewen, Stephan Schlemmer, Michael C McCarthy
RB09
11:16 – 11:31
FT-IR MEASUREMENTS OF NH3 LINE INTENSITIES IN THE 60 – 550 CM−1 USING SOLEIL/AILES BEAMLINE,
Keeyoon Sung, Shanshan Yu, John Pearson, Laurent Manceron, F. Kwabia Tchana, Olivier Pirali
RB10
11:33 – 11:48
THE H2 O-CH3 F COMPLEX: A COMBINED MICROWAVE AND INFRARED SPECTROSCOPIC STUDY SUPPORTED
BY STRUCTURE CALCULATIONS, Sharon Priya Gnanasekar, Manuel Goubet, Elangannan Arunan, Robert Georges, Pascale Soulard, Pierre Asselin, T. R. Huet, Olivier Pirali
RC. Mini-symposium: Spectroscopy in the Classroom
25
Chair: Kristopher J Ooms, The King’s University, Edmonton, Alberta, Canada
ar
y
RC01
INVITED TALK
8:30 – 9:00
DIRECT DIGITAL SYNTHESIS CHIRPED PULSE MICROWAVE SPECTROMETERS FOR THE CLASSROOM AND
RESEARCH, Geoffrey Blake, Brandon Carroll, Ian A Finneran
RC02
9:05 – 9:20
A SIMPLE, COST EFFECTIVE RAMAN-FLUORESCENCE SPECTROMETER FOR USE IN LABORATORY AND
FIELD EXPERIMENTS, Frank E Marshall, Michael A Pride, Michellle Rojo, Katelyn R. Brinker, Zachary Walker, Michael
Storrie-Lombardi, Melanie R. Mormile, G. S. Grubbs II
RC03
9:22 – 9:37
LIF AND RAMAN SPECTROSCOPY IN UNDERGRADUATE LABS USING GREEN DIODE-PUMPED SOLID-STATE
LASERS, Jeffrey A. Gray
in
RC04
9:39 – 9:54
SPECFITTER: A LEARNING ENVIRONMENT FOR THE ROTATIONAL SPECTROSCOPIST, Yoon Jeong Choi, Weixin
Wu, A. J. Minei, S. A. Cooke
RC05
9:56 – 10:11
APPLICATIONS OF GROUP THEORY: INFRARED AND RAMAN SPECTRA OF THE ISOMERS OF cis- AND trans1,2-DICHLOROETHYLENE, Norman C. Craig
Pr
el
im
Intermission
RC06
10:30 – 10:40
INFRARED ANALYSIS OF COMBUSTION PRODUCTS AND INTERMEDIATES OF HYDROCARBON COMBUSTION FOR SEVERAL SPECIES, Allen White, Rebecca Devasher
RC07
10:42 – 10:52
CHIRPED-PULSE MICROWAVE SPECTROSCOPY IN THE UNDERGRADUATE CHEMISTRY CURRICULUM,
Sydney A Gaster, Taylor M Hall, Sean Arnold, Gordon G Brown
RC08
10:54 – 11:04
USB SPECTROMETERS AND THE TEMPERATURE OF THE SUN: MEASURING BLACK BODY RADIATION IN
THE PALM OF YOUR HAND, Daniel P. Zaleski, Benjamin R Horrocks, Nick Walker
RC09
11:06 – 11:16
VIBRATION-ROTATION ANALYSIS OF THE 13 CO2 ASYMMETRIC STRETCH FUNDAMENTAL BAND IN AMBIENT AIR FOR THE PHYSICAL CHEMISTRY TEACHING LABORATORY, David A Dolson, CATHERINE B ANDERS
RC10
11:18 – 11:33
UTILIZING SPECTROSCOPIC RESEARCH TOOLS AND SOFTWARE IN THE CLASSROOM, G. S. Grubbs II
26
RD. Astronomy
Chair: Brett A. McGuire, California Institute of Technology, Pasadena, CA, USA
ar
y
RD01
8:30 – 8:40
NEW INSTRUMENTAL TOOLS FOR ADVANCED ASTROCHEMICAL APPLICATIONS, Amanda Steber, Sabrina Zinn,
Melanie Schnell, Anouk Rijs
RD02
8:42 – 8:57
DOPPLER AND SUB-DOPPLER MILLIMETER AND SUB-MILLIMETER WAVE SPECTROSCOPY OF KEY ASTRONOMICAL MOLECULES: HNC AND CS, Oliver Zingsheim, Thomas Schmitt, Frank Lewen, Stephan Schlemmer,
Sven Thorwirth
RD03
8:59 – 9:14
MILLIMETRE-WAVE SPECTRUM OF ISOTOPOLOGUES OF ETHANOL FOR RADIO ASTRONOMY, Adam Walters,
Mirko Schäfer, Matthias H. Ordu, Frank Lewen, Stephan Schlemmer, Holger S. P. Müller
OF
DEUTERATED
METHYLENE
BI-RADICAL,
in
RD04
TERAHERTZ SPECTROSCOPY
Stephane Bailleux
RD05
THZ SPECTROSCOPY OF D2 H+ , Shanshan Yu, John Pearson, Takayoshi Amano
CD2 ,
9:16 – 9:31
Hiroyuki Ozeki,
9:33 – 9:48
Pr
el
im
RD06
9:50 – 10:05
THZ SPECTROSCOPY OF 12 CH+ , 13 CH+ , AND 12 CD+ , Shanshan Yu, Brian Drouin, John Pearson, Takayoshi Amano
RD07
10:07 – 10:22
ROTATIONAL SPECTROSCOPY OF VIBRATIONALLY EXCITED N2 H+ and N2 D+ UP TO 2 THZ, Shanshan Yu, John
Pearson, Brian Drouin, Timothy J Crawford, Adam M Daly, Ben Elliott, Takayoshi Amano
Intermission
RD08
10:41 – 10:56
NEW ACCURATE WAVENUMBERS OF H35 Cl+ AND H37 Cl+ ROVIBRATIONAL TRANSITIONS IN THE v = 0 − 1
BAND OF THE 2 Π STATE., Jose Luis Domenech, Maite Cueto, Victor Jose Herrero, Isabel Tanarro, Jose Cernicharo
RD09
10:58 – 11:13
OSCILLATOR STRENGTHS AND PREDISSOCIATION RATES FOR W − X BANDS AND THE 4P5P COMPLEX IN
13 18
C O, Michele Eidelsberg, Jean Louis Lemaire, Steven Federman, Glenn Stark, Alan Heays, Lisseth Gavilan, James R
Lyons, Peter L Smith, Nelson de Oliveira, Denis Joyeux
RD10
11:15 – 11:30
LINE STRENGTHS OF ROVIBRATIONAL AND ROTATIONAL TRANSITIONS IN THE X2 Π GROUND STATE OF OH,
James S.A. Brooke, Peter F. Bernath, Colin Western, Chris Sneden, Gang Li, Iouli E Gordon
RD11
11:32 – 11:42
CLASS I METHANOL MASER CONDITIONS NEAR SNRS, Bridget C. McEwen, Ylva M. Pihlström, Loránt O. Sjouwerman
RD12
11:44 – 11:59
THE MISSING LINK: ROTATIONAL SPECTRUM AND GEOMETRICAL STRUCTURE OF DISILICON CARBIDE,
Si2 C, Michael C McCarthy, Joshua H Baraban, Bryan Changala, John F. Stanton, Marie-Aline Martin-Drumel, Sven Thorwirth, Neil J Reilly, Carl A Gottlieb
27
RE. Instrument/Technique Demonstration
Chair: Arthur Suits, Wayne State University, Detroit, MI, USA
ar
y
RE01
8:30 – 8:45
OPTIMIZATION OF EXTREME ULTRAVIOLET LIGHT SOURCE FROM HIGH HARMONIC GENERATION FOR
CONDENSED-PHASE CORE-LEVEL SPECTROSCOPY, Ming-Fu Lin, Max A Verkamp, Elizabeth S Ryland, Kristin
Benke, Kaili Zhang, Michaela Carlson, Josh Vura-Weis
RE02
8:47 – 9:02
DEVELOPMENT OF TWO-PHOTON PUMP POLARIZATION SPECTROSCOPY PROBE TECHNIQUE (TPP-PSP) FOR
MEASUREMENTS OF ATOMIC HYDROGEN . , Aman Satija, Robert P. Lucht
RE03
9:04 – 9:19
DEVELOPMENT OF COMBINED DUAL-PUMP VIBRATIONAL AND PURE-ROTATIONAL COHERENT ANTISTOKES RAMAN SCATTERING TECHNIQUE., Aman Satija, Robert P. Lucht
in
RE04
9:21 – 9:36
VELOCITY MAP IMAGING STUDY OF THE PHOTOINITIATED CHARGE-TRANSFER DISSOCIATION OF
Cu+ (C6 H6 ) AND Ag+ (C6 H6 ), Jon Maner, Daniel Mauney, Michael A Duncan
Intermission
Pr
el
im
RE05
9:55 – 10:10
MID-IR CAVITY RINGDOWN SPECTROSCOPY FOR ATMOSPHERIC ETHANE ABUNDANCE MEASUREMENTS,
Linhan Shen, Thinh Quoc Bui, Lance Christensen, Mitchio Okumura
RE06
10:12 – 10:27
STRONG THERMAL NONEQUILIBRIUM IN HYPERSONIC CO AND CH4 PROBED BY CRDS, Maud Louviot, Nicolas
Suas-David, Vincent Boudon, Robert Georges, Michael Rey, Samir Kassi
RE07
ROTATIONALLY-RESOLVED INFRARED SPECTROSCOPY
Bradley M. Gibson, Nicole Koeppen, Benjamin J. McCall
OF
THE
ν16
BAND
OF
10:29 – 10:44
1,3,5-TRIOXANE,
RE08
10:46 – 11:01
IMPROVING SNR IN TIME-RESOLVED SPECTROSCOPIES WITHOUT SACRIFICING TEMPORAL-RESOLUTION:
APPLICATION TO THE UV PHOTOLYSIS OF METHYL CYANOFORMATE, Michael J. Wilhelm, Jonathan M. Smith,
HAI-LUNG Dai
RE09
11:03 – 11:18
LASER-INDUCED PLASMAS IN AMBIENT AIR FOR INCOHERENT BROADBAND CAVITY-ENHANCED ABSORPTION SPECTROSCOPY , Albert A Ruth, Sophie Dixneuf, Johannes Orphal
28
RF. Atmospheric science
Thursday, June 25, 2015 – 1:30 PM
Chair: Joseph Hodges, National Institute of Standards and Technology, Gaithersburg, MD, USA
ar
y
RF01
1:30 – 1:40
PHOTOACOUSTIC SPECTROSCOPY OF THE OXYGEN A-BAND, Elizabeth M Lunny, Thinh Quoc Bui, Caitlin Bray,
Priyanka Rupasinghe, Mitchio Okumura
RF02
1:42 – 1:57
HIGH PRESSURE OXYGEN A-BAND SPECTRA, Brian Drouin, Keeyoon Sung, Shanshan Yu, Elizabeth M Lunny, Thinh
Quoc Bui, Mitchio Okumura, Priyanka Rupasinghe, Caitlin Bray, David A. Long, Joseph Hodges, David Robichaud, D. Chris
Benner, V. Malathy Devi, Jiajun Hoo
RF03
1:59 – 2:14
COLLISION-DEPENDENT LINE AREAS IN THE a1 ∆g ← X 3 Σ−
BAND
OF
MOLECULAR
OXYGEN,
Vincent
Sirong
neau, Adam J. Fleisher, Joseph Hodges
in
RF04
2:16 – 2:31
ANOMALOUS CENTRIFUGAL DISTORTION IN HDO AND SPECTROSCOPIC DATA BASES, L. H. Coudert
RF05
2:33 – 2:48
SPEED-DEPENDENT BROADENING AND LINE-MIXING IN CH4 PERTURBED BY AIR NEAR 1.64 µm FOR THE
FRENCH/GERMAN CLIMATE MISSION MERLIN, Thibault Delahaye, Thi Ngoc Ha Tran, Zachary Reed, Stephen E
Maxwell, Joseph Hodges
Pr
el
im
RF06
2:50 – 3:05
MID INFRARED DUAL FREQUENCY COMB SPECTROMETER FOR THE DETECTION OF METHANE IN AMBIENT AIR , Hans Schuessler, Feng Zhu, Alexander Kolomenskii
RF07
3:07 – 3:22
IMPROVED OZONE AND CARBON MONOXIDE PROFILE RETRIEVALS USING MULTISPECTRAL MEASUREMENTS FROM NASA “A TRAIN”, NPP, AND TROPOMI SATELLITES, Dejian Fu
RF08
3:24 – 3:39
TEMPERATURE DEPENDENCES OF AIR-BROADENING AND SHIFT PARAMETERS IN THE ν3 BAND OF OZONE,
Mary Ann H. Smith, V. Malathy Devi, D. Chris Benner
Intermission
RF09
3:58 – 4:13
MICROWAVE OPTICAL DOUBLE RESONANCE STUDIES OF PERTURBATIONS IN THE SO A3 Π STATE, Andrew Richard Whitehill, Alexander W. Hull, Trevor J. Erickson, Jun Jiang, Carrie Womack, Barratt Park, Shuhei Ono,
Robert W Field
RF10
4:15 – 4:30
VALIDATION OF A NEW HNO3 LINE PARAMETERS AT 7.6 µm USING LABORATORY INTENSITY MEASUREMENTS AND MIPAS SATELLITE SPECTRA, Marco Ridolfi, Agnes Perrin, Jean-Marie Flaud, Jean Vander Auwera, Massimo Carlotti
RF11
4:32 – 4:47
ROTATIONAL SPECTROSCOPY OF NEWLY DETECTED ATMOSPHERIC OZONE DEPLETERS: CF3 CH2 Cl,
CF3 CCl3 , AND CF2 ClCCl3 , Zbigniew Kisiel, Ewa Białkowska-Jaworska, Lech Pszczółkowski, Iciar Uriarte, Patricia Ecija,
Francisco J. Basterretxea, Emilio J. Cocinero
RF12
4:49 – 5:04
CHIRPED PULSE AND CAVITY FT MICROWAVE SPECTROSCOPY OF THE FORMIC ACID – TRIMETHYLAMINE
WEAKLY BOUND COMPLEX, Becca Mackenzie, Chris Dewberry, Ken Leopold
RF13
5:06 – 5:21
FORMIC SULFURIC ANHYDRIDE: A NEW CHEMICAL SPECIES WITH POSSIBLE IMPLICATIONS FOR ATMOSPHERIC AEROSOL, Becca Mackenzie, Chris Dewberry, Ken Leopold
RF14
5:23 – 5:38
ROTATIONAL SPECTROSCOPY OF METHYL VINYL KETONE, Olena Zakharenko, R. A. Motiyenko, Juan-Ramon
Aviles Moreno, T. R. Huet
RF15
5:40 – 5:55
THE MILLIMETER-WAVE SPECTRUM OF METHACROLEIN. TORSION-ROTATION-VIBRATION EFFECTS IN THE
EXCITED STATES, Olena Zakharenko, R. A. Motiyenko, Juan-Ramon Aviles Moreno, T. R. Huet
29
RG. Vibrational structure/frequencies
Chair: John F. Stanton, The University of Texas, Austin, TX, USA
ar
y
RG01
1:30 – 1:45
ALKYL CH STRETCH VIBRATIONS AS A PROBE OF LOCAL ENVIRONMENT AND STRUCTURE, Edwin Sibert,
Daniel P. Tabor, Nathanael Kidwell, Jacob C. Dean, Timothy S. Zwier
RG02
1:47 – 2:02
COMPUTING THE VIBRATIONAL ENERGIES OF CH2 O AND CH3 CN WITH PHASE-SPACED LOCALIZED FUNCTIONS AND AN ITERATIVE EIGENSOLVER, James Brown, Tucker Carrington
RG03
2:04 – 2:19
A MULTILAYER SUM-OF-PRODUCTS METHOD FOR COMPUTING VIBRATIONAL SPECTRA WITHOUT STORING FULL-DIMENSIONAL VECTORS OR MATRCIES, Phillip Thomas, Tucker Carrington
in
RG04
2:21 – 2:36
QUANTUM MONTE CARLO ALGORITHMS FOR DIAGRAMMATIC VIBRATIONAL STRUCTURE CALCULATIONS, Matthew Hermes, So Hirata
RG05
DIAGRAMMATIC VIBRATIONAL COUPLED-CLUSTER, Jacob A Faucheaux, So Hirata
2:38 – 2:53
Pr
el
im
RG06
2:55 – 3:10
VIBRATIONAL JAHN-TELLER EFFECT IN NON-DEGENERATE ELECTRONIC STATES, Mahesh B. Dawadi,
Bishnu P Thapaliya, Ram Bhatta, David S. Perry
RG07
3:12 – 3:27
SPECTRAL SIGNATURES AND STRUCTURAL MOTIFS IN NEUTRAL AND PROTONATED HISTAMINE: A COMPUTATIONAL STUDY , Santosh Kumar Srivastava, Vipin Bahadur Singh
RG08
3:29 – 3:39
ANALOG OF DUSCHINSKY MATRIX AND CO-ASSIGNMENT OF FREQUENCIES IN DIFFERENT ELECTRONIC
STATES, Yurii Panchenko, Alexander Abramenkov
Intermission
RG09
3:58 – 4:13
HIGH RESOLUTION INFRARED SPECTRA OF TRIACETYLENE, Kirstin D Doney, Dongfeng Zhao, Harold Linnartz
RG10
4:15 – 4:30
INFRARED AND ULTRAVIOLET SPECTROSCOPY OF GAS-PHASE IMIDAZOLIUM AND PYRIDINIUM IONIC
LIQUIDS., Justin W. Young, Ryan S Booth, Christopher Annesley, Jaime A. Stearns
RG11
4:32 – 4:47
GROUND AND EXCITED STATE ALKYL CH STRETCH IR SPECTRA OF STRAIGHT-CHAIN ALKYLBENZENES,
Daniel M. Hewett, Joseph A. Korn, Timothy S. Zwier
RG12
4:49 – 5:04
ASYMMETRY OF M+ (H2 O)RG COMPLEXES, (M=V, Nb) REVEALED WITH INFRARED SPECTROSCOPY,
TIMOTHY B WARD, Evangelos Miliordos, Sotiris Xantheas, Michael A Duncan
RG13
5:06 – 5:21
INFRARED SPECTROSCOPY OF PROTONATED ACETYLACETONE AND MIXED ACETYLACETONE/WATER
CLUSTERS, Daniel Mauney, Jon Maner, David C McDonald II, Michael A Duncan
RG14
HEAVY ATOM VIBRATIONAL MODES AND LOW-ENERGY VIBRATIONAL AUTODETACHMENT IN
NITROMETHANE ANIONS, Michael C Thompson, Joshua H Baraban, John F. Stanton, J. Mathias Weber
5:23 – 5:38
RG15
5:40 – 5:55
OBSERVATION OF DIPOLE-BOUND STATE AND HIGH-RESOLUTION PHOTOELECTRON IMAGING OF COLD
ACETATE ANIONS, Guo-Zhu Zhu, Dao-Ling Huang, Lai-Sheng Wang
30
RH. Clusters/Complexes
Chair: Galen Sedo, University of Virginia’s College at Wise, Wise, VA, USA
ar
y
RH01
1:30 – 1:45
CHIRPED PULSE AND CAVITY FT MICROWAVE SPECTROSCOPY OF THE HCCH-2,6-DIFLUOROPYRIDINE
WEAKLY BOUND COMPLEX, Chris Dewberry, Becca Mackenzie, Ken Leopold
RH02
1:47 – 1:57
MICROWAVE SPECTRUM, VAN DER WAALS BOND LENGTH, AND 131 Xe QUADRUPOLE COUPLING CONSTANT
OF Xe-SO3 , Chris Dewberry, Anna Huff, Becca Mackenzie, Ken Leopold
RH03
1:59 – 2:14
DIMETHYL SULFIDE-DIMETHYL ETHER AND ETHYLENE OXIDE-ETHYLENE SULFIDE COMPLEXES INVESTIGATED BY FOURIER TRANSFORM MICROWAVE SPECTROSCOPY AND AB INITIO CALCULATION,
Yoshiyuki Kawashima, Yoshio Tatamitani, Takayuki Mase, Eizi Hirota
in
RH04
2:16 – 2:31
INTERNAL DYNAMICS IN SF6 ···NH3 OBSERVED BY BROADBAND ROTATIONAL SPECTROSCOPY,
Dror M. Bittner, Daniel P. Zaleski, Susanna L. Stephens, Nick Walker, Anthony Legon
RH05
2:33 – 2:48
EVIDENCE FOR A COMPLEX BETWEEN THF AND ACETIC ACID FROM BROADBAND ROTATIONAL SPECTROSCOPY, Daniel P. Zaleski, Dror M. Bittner, John Connor Mullaney, Susanna L. Stephens, Adrian King, Matthew Habgood, Nick Walker
Pr
el
im
RH06
2:50 – 3:00
THE ROTATIONAL SPECTRUM OF PYRIDINE-FORMIC ACID, Lorenzo Spada, Qian Gou, Barbara Michela Giuliano,
Walther Caminati
Intermission
RH07
3:19 – 3:34
FOURIER-TRANSFORM MICROWAVE AND MILLIMETERWAVE SPECTROSCOPY OF THE H2 -HCN MOLECULAR
COMPLEX, Keiichi Tanaka, Kensuke Harada, Yoshihiro Sumiyoshi, Masakazu Nakajima, Yasuki Endo
RH08
3:36 – 3:51
MICROWAVE SPECTROSCOPY OF THE CYCLOPENTANOL - WATER DIMER, Brandon Carroll, Ian A Finneran, Geoffrey Blake
RH09
3:53 – 4:08
HYDROGEN-BONDING AND HYDROPHOBIC INTERACTIONS IN THE ETHANOL-WATER DIMER, Ian A Finneran,
Brandon Carroll, Marco A. Allodi, Geoffrey Blake
RH10
4:10 – 4:25
THE INFLUENCE OF FLUORINATION ON STRUCTURE OF THE TRIFLUOROACETONITRILE WATER COMPLEX,
Wei Lin, Anan Wu, Xin Lu, Daniel A. Obenchain, Stewart E. Novick
RH11
4:27 – 4:42
THE POSITION OF DEUTERIUM IN THE HOD − N2 O AS DETERMINED BY STRUCTURAL AND NUCLEAR
QUADRUPOLE COUPLING CONSTANTS, Daniel A. Obenchain, Derek S. Frank, Stewart E. Novick, William Klemperer
RH12
4:44 – 4:59
THE CP-FTMW SPECTROSCOPY AND ASSIGNMENT OF THE MONO- AND DIHYDRATE COMPLEXES OF PERFLUOROPROPIONIC ACID, G. S. Grubbs II, Daniel A. Obenchain, Derek S. Frank, Stewart E. Novick, S. A. Cooke,
Agapito Serrato III, Wei Lin
RH13
5:01 – 5:16
HYDROGEN BONDING IN 4-AMINOPHENYL ETHANOL: A COMBINED IR-UV DOUBLE RESONANCE AND MICROWAVE STUDY, Caitlin Bray, Cara Rae Rivera, E. A. Arsenault, Daniel A. Obenchain, Stewart E. Novick, Joseph L.
Knee
RH14
5:18 – 5:28
THEORETICAL STUDY OF THE EFFECT OF DOPING CLUSTERS (ZNO) 6 BY THE SELENIUM USING THE DFT,
Nour el Houda Bensiradj, Ourida Ouamerali
RH15
5:30 – 5:45
BORONYL MIMICS GOLD: A PHOTOELECTRON SPECTROSCOPY STUDY, Tian Jian, Gary Lopez, Lai-Sheng Wang
RI. Astronomy
31
Chair: Harshal Gupta, California Institute of Technology, Pasadena, CA, USA
ar
y
RI01
1:30 – 1:45
THE COMPLETE, TEMPERATURE RESOLVED SPECTRUM OF METHYL FORMATE BETWEEN 214 AND 265 GHZ,
James P. McMillan, Sarah Fortman, Christopher F. Neese, Frank C. De Lucia
RI02
1:47 – 2:02
ROTATIONAL SPECTROSCOPY OF 4-HYDROXY-2-BUTYNENITRILE, R. A. Motiyenko, L. Margulès, J.-C. Guillemin
RI03
2:04 – 2:19
TIME-DOMAIN TERAHERTZ SPECTROSCOPY OF ISOLATED PAHS , Brandon Carroll, Marco A. Allodi, Brett A.
McGuire, Sergio Ioppolo, Geoffrey Blake
in
RI04
2:21 – 2:36
HIGH-RESOLUTION IR ABSORPTION SPECTROSCOPY OF POLYCYCLIC AROMATIC HYDROCARBONS: SHINING LIGHT ON THE INTERSTELLAR 3 MICRON EMISSION BANDS, Elena Maltseva, Alessandra Candian, Xander
Tielens, Annemieke Petrignani, J. Oomens, Wybren Jan Buma
RI05
2:38 – 2:53
EXPLORING MOLECULAR COMPLEXITY WITH ALMA (EMoCA): HIGH-ANGULAR-RESOLUTION OBSERVATIONS OF SAGITTARIUS B2(N) AT 3 mm, Holger S. P. Müller, Arnaud Belloche, Karl M. Menten, Robin T. Garrod
Pr
el
im
RI06
2:55 – 3:10
FIRST SPECTROSCOPIC STUDIES AND DETECTION IN SgrB2 OF 13 C-DOUBLY SUBSTITUED ETHYL CYANIDE,
L. Margulès, R. A. Motiyenko, J.-C. Guillemin, Holger S. P. Müller, Arnaud Belloche
RI07
3:12 – 3:27
MILLIMETERWAVE SPECTROSCOPY OF ETHANIMINE AND PROPANIMINE AND THEIR SEARCH IN ORION,
L. Margulès, R. A. Motiyenko, J.-C. Guillemin, Jose Cernicharo
Intermission
RI08
3:46 – 4:01
FURTHER STUDIES OF λ 5797.1 DIFFUSE INTERSTELLAR BAND, Takeshi Oka, L. M. Hobbs, Daniel E. Welty, Donald
G. York, Julie Dahlstrom, Adolf N. Witt
RI09
4:03 – 4:18
LABORATORY OPTICAL SPECTROSCOPY OF THE PHENOXY RADICAL AS A DIFFUSE INTERSTELLAR BANDS
CANDIDATE, Mitsunori Araki, Yuki MATSUSHITA, Koichi Tsukiyama
RI10
4:20 – 4:35
INVESTIGATION OF CARBONACEOUS INTERSTELLAR DUST ANALOGUES BY INFRARED SPECTROSCOPY:
EFFECTS OF ENERGETIC PROCESSING, Belén Maté, Miguel Jiménez-Redondo, Isabel Tanarro, Victor Jose Herrero
RI11
4:37 – 4:52
REACTIONS OF GROUND STATE NITROGEN ATOMS N(4 S) WITH ASTROCHEMICALLY-RELEVANT
MOLECULES ON INTERSTELLAR DUSTS, Lahouari Krim, Sendres Nourry
RI12
4:54 – 5:09
STABILITY OF GLYCINE TO ENERGETIC PROCESSING UNDER ASTROPHYSICAL CONDITIONS INVESTIGATED VIA INFRARED SPECTROSCOPY, Belén Maté, Victor Jose Herrero, Isabel Tanarro, Rafael Escribano
RI13
5:11 – 5:21
MILLIMETER AND SUBMILLIMETER STUDIES OF INTERSTELLAR ICE ANALOGUES, AJ Mesko, Ian C Wagner,
Houston Hartwell Smith, Stefanie N Milam, Susanna L. Widicus Weaver
RI14
5:23 – 5:38
UNTANGLING MOLECULAR SIGNALS OF ASTROCHEMICAL ICES IN THE THz: DISTINGUISHING AMORPHOUS, CRYSTALLINE, AND INTRAMOLECULAR MODES WITH BROADBAND THz SPECTROSCOPY,
Brett A. McGuire, Sergio Ioppolo, Xander de Vries, Marco A. Allodi, Brandon Carroll, Geoffrey Blake
RI15
5:40 – 5:55
QUANTUM CHEMICAL STUDY OF THE REACTION OF C+ WITH INTERSTELLAR ICE: PREDICTIONS OF VIBRATIONAL AND ELECTRONIC SPECTRA OF REACTION PRODUCTS, David E. Woon
32
RJ. Cold/Ultracold/Matrices/Droplets
Chair: Gary E. Douberly, The University of Georgia, Athens, GA, USA
ar
y
RJ01
1:30 – 1:45
IR SPECTRA OF COLD PROTONATED METHANE, Oskar Asvany, Koichi MT Yamada, Sandra Brünken, Alexey Potapov,
Stephan Schlemmer
RJ02
1:47 – 2:02
PROGRESS ON OPTICAL ROTATIONAL COOLING OF SiO+, Patrick R Stollenwerk, Yen-Wei Lin, Brian C. Odom
RJ03
2:04 – 2:19
THE OPTICAL BICHROMATIC FORCE IN MOLECULAR SYSTEMS, Leland M. Aldridge, Scott E. Galica,
Edward E. Eyler
RJ04
2:21 – 2:36
A NEW EQUATION OF STATE FOR SOLID para-HYDROGEN, Lecheng Wang, Robert J. Le Roy, Pierre-Nicholas Roy
in
RJ05
2:38 – 2:53
INFRARED SPECTROSCOPY OF NOH SUSPENDED IN SOLID PARAHYDROGEN: PART TWO, Morgan E. Balabanoff, Fredrick M. Mutunga, David T. Anderson
RJ06
2:55 – 3:10
HIGH RESOLUTION INFRARED SPECTROSCOPY OF CH3 F-(ortho-H2 )n CLUSTER IN SOLID para-H2 ,
Hiroyuki Kawasaki, Asao Mizoguchi, Hideto Kanamori
Pr
el
im
Intermission
RJ07
3:29 – 3:44
REACTIVE INTERMEDIATES IN 4 He NANODROPLETS: INFRARED LASER STARK SPECTROSCOPY OF DIHYDROXYCARBENE, Bernadette M. Broderick, Christopher P. Moradi, Gary E. Douberly, Laura McCaslin, John F. Stanton
RJ08
3:46 – 4:01
INFRARED LASER STARK SPECTROSCOPY OF THE PRE-REACTIVE Cl···HCl COMPLEX FORMED IN SUPERFLUID 4 He DROPLETS, Christopher P. Moradi, Gary E. Douberly
RJ09
4:03 – 4:13
HELIUM NANODROPLET INFRARED SPECTROSCOPY OF THE TROPYL RADICAL, Matin Kaufmann, Bernadette
M. Broderick, Gary E. Douberly
RJ10
4:15 – 4:30
MICROSOLVATION STUDIES IN HELIUM NANODROPLETS, Gerhard Schwaab, Matin Kaufmann, Daniel Leicht, Raffael Schwan, Theo Fischer, Devendra Mani, Martina Havenith
RJ11
4:32 – 4:47
INFRARED SPECTRA OF THE CO2 -H2 O, CO2 -(H2 O)2 , and (CO2 )2 -H2 O COMPLEXES ISOLATED IN SOLID NEON
BETWEEN 90 AND 5300 cm−1 , Benoı̂t Tremblay, Pascale Soulard
RJ12
4:49 – 4:59
MATRIX ISOLATION AND COMPUTATIONAL STUDY OF [2C, 2N, X] (X=S, SE) ISOMERS, Tamas Voros, Gyorgy
Tarczay
RJ13
5:01 – 5:16
MATRIX ISOLATION SPECTROSCOPY AND PHOTOCHEMISTRY OF TRIPLET 1,3-DIMETHYLPROPYNYLIDENE
(MeC3 Me), Stephanie N. Knezz, Terese A Waltz, Benjamin C. Haenni, Nicola J. Burrmann, Robert J. McMahon
RJ14
5:18 – 5:33
EVIDENCE OF INTERNAL ROTATION IN THE O-H STRETCHING REGION OF THE 1:1 METHANOL-BENZENE
COMPLEX IN AN ARGON MATRIX, Jay Amicangelo, Ian Campbell, Joshua Wilkins
FA. Electronic structure, potential energy surfaces
33
Friday, June 26, 2015 – 8:30 AM
Chair: Timothy Steimle, Arizona State University, Tempe, AZ, USA
ar
y
FA01
8:30 – 8:45
CHARACTERIZATION OF THE 1 5 Πu - 1 5 Πg BAND OF C2 BY TWO-COLOR RESONANT FOUR-WAVE MIXING
AND LIF, Peter Radi
FA02
8:47 – 9:02
SIGN CHANGES IN THE ELECTRIC DIPOLE MOMENT OF EXCITED STATES IN RUBIDIUM-ALKALINE EARTH
DIATOMIC MOLECULES, Johann V. Pototschnig, Florian Lackner, Andreas W. Hauser, Wolfgang E. Ernst
FA03
9:04 – 9:19
HIGH RESOLUTION VELOCITY MAP IMAGING PHOTOELECTRON SPECTROSCOPY OF THE BERYLLIUM OXIDE ANION, BEO-, Amanda Reed, Kyle Mascaritolo, Michael Heaven
in
FA04
9:21 – 9:36
ELECTRONIC AUTODETACHMENT SPECTROSCOPY AND IMAGING OF THE ALUMINUM MONOXIDE ANION,
ALO-, Amanda Reed, Kyle Mascaritolo, Adrian Gardner, Michael Heaven
FA05
9:38 – 9:53
SPECTROSCOPY OF THE LOW-ENERGY STATES OF BaO+ , Joshua Bartlett, Robert A. VanGundy, Michael Heaven
Intermission
Pr
el
im
FA06
10:12 – 10:27
THE OPTICAL SPECTRUM OF SrOH RE-VISITED: ZEEMAN EFFECT, HIGH-RESOLUTION SPECTROSCOPY AND
FRANCK-CONDON FACTORS. , Trung Nguyen, Damian L Kokkin, Timothy Steimle, Ivan Kozyryev, John M. Doyle
FA07
10:29 – 10:44
SPECTROSCOPIC ACCURACY IN QUANTUM CHEMISTRY: A BENCHMARK STUDY ON Na3 , Andreas W. Hauser,
Johann V. Pototschnig, Wolfgang E. Ernst
FA08
10:46 – 11:01
ACCURATE FIRST-PRINCIPLES SPECTRA PREDICTIONS FOR ETHYLENE AND ITS ISOTOPOLOGUES FROM
FULL 12D AB INITIO SURFACES, Thibault Delahaye, Michael Rey, Vladimir Tyuterev, Andrei V. Nikitin, Peter Szalay
FA09
11:03 – 11:18
HIGH-RESOLUTION LASER SPECTROSCOPY OF S1 -S0 TRANSITION OF NAPHTHALENE: MEASUREMENT OF
VIBRATIONALLY EXCITED STATES, Takumi Nakano, Ryo Yamamoto, Shunji Kasahara
FA10
HIGH-RESOLUTION LASER SPECTROSCOPY OF THE S1
Shunji Kasahara, Ryo Yamamoto
11:20 – 11:35
← S0 TRANSITION OF Cl-NAPHTHALENES,
34
FB. Spectroscopy as an analytical tool
Friday, June 26, 2015 – 8:30 AM
Chair: Christopher F. Neese, The Ohio State University, Columbus, OH, USA
FB02
MEDIUM RESOLUTION CAVITY SPECTROSCOPY FOR
Satyakumar Nagarajan, Christopher F. Neese, Frank C. De Lucia
ar
y
FB01
8:30 – 8:45
CONTINUOUS MONITORING OF PHOTOLYSIS PRODUCTS BY THZ SPECTROSCOPY, Abdelaziz Omar,
Arnaud Cuisset, Gaël Mouret, Francis Hindle, Sophie Eliet, Robin Bocquet
THE
STUDY
OF
LARGE
8:47 – 9:02
MOLECULES,
FB03
9:04 – 9:19
SUBMILLIMETER/INFRARED DOUBLE RESONANCE: REGIMES FOR MOLECULAR SENSORS, Sree Srikantaiah,
Ivan Medvedev, Christopher F. Neese, Dane Phillips, Henry O. Everitt, Frank C. De Lucia
in
FB04
9:21 – 9:36
ROTATIONAL SPECTROSCOPY AS A TOOL TO INVESTIGATE INTERACTIONS BETWEEN VIBRATIONAL
POLYADS IN SYMMETRIC TOP MOLECULES: LOW-LYING STATES v8 ≤ 2 OF METHYL CYANIDE,
Holger S. P. Müller, Matthias H. Ordu, Frank Lewen, Linda Brown, Brian Drouin, John Pearson, Keeyoon Sung, Isabelle
Kleiner, Robert Sams
FB05
9:38 – 9:53
VIBRATIONAL SUM FREQUENCY STUDY OF THE INFLUENCE OF WATER-IONIC LIQUID MIXTURES IN THE
CO2 ELECTROREDUCTION ON SILVER ELECTRODES, Natalia Garcia Rey, Dana Dlott
Pr
el
im
Intermission
FB06
10:12 – 10:27
ELUCIDATING THE COMPLEX LINESHAPES RESULTING FROM THE HIGHLY SENSITIVE, ION SELECTIVE,
TECHNIQUE NICE-OHVMS, James N. Hodges, Brian Siller, Benjamin J. McCall
FB07
10:29 – 10:44
CHARACTERIZATION AND INFRARED EMISSION SPECTROSCOPY OF BALL PLASMOID DISCHARGES,
Scott E. Dubowsky, Benjamin J. McCall
FB08
10:46 – 11:01
VUV FLUORESCENCE OF WATER & AMMONIA FOR SATELLITE THRUSTER PLUME CHARACTERIZATION.,
Justin W. Young, Christopher Annesley, Ryan S Booth, Jaime A. Stearns
FB09
11:03 – 11:18
REACTIONS OF 3-OXETANONE AT HIGH TEMPERATURES, Emily Wright, Brian Warner, Hannah Foreman, Kimberly
N. Urness, Laura R. McCunn
FC. Comparing theory and experiment
35
Friday, June 26, 2015 – 8:30 AM
Chair: Edwin Sibert, The Univeristy of Wisconsin, Madison, WI, USA
ar
y
FC01
8:30 – 8:45
VIBRATIONAL COUPLING IN SOLVATED FORM OF EIGEN PROTON, Jheng-Wei Li, Kaito Takahashi, Jer-Lai Kuo
FC02
8:47 – 9:02
BINDING BETWEEN NOBEL GAS ATOMS AND PROTONATED WATER MONOMER AND DIMER, Ying-Cheng Li,
Jer-Lai Kuo
FC03
9:04 – 9:19
ANALYSIS OF HYDROGEN BONDING IN THE OH STRETCH REGION OF PROTONATED WATER CLUSTERS,
Laura C. Dzugan, Anne B McCoy
in
FC04
9:21 – 9:36
SEMIEXPERIMENTAL STRUCTURE OF THE NON-RIGID BF2 OH MOLECULE BY COMBINING HIGH RESOLUTION INFRARED SPECTROSCOPY AND AB INITIO CALCULATIONS. , Natalja Vogt, Jean Demaison, Agnes Perrin,
Hans Bürger
FC05
9:38 – 9:48
CONFORMATIONAL, VIBRATIONAL AND ELECTRONIC PROPERTIES OF C5H3XOS (X = H, F, Cl OR Br): HALOGEN AND SOLVENT EFFECTS , Mustafa Senyel, Gunes Esma, Cemal Parlak
Pr
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FC06
9:50 – 10:05
COMBINED EXPERIMENTAL AND THEORETICAL STUDIES ON THE VIBRATIONAL AND ELECTRONIC SPECTRA OF 5-QUINOLINECARBOXALDEHYDE, Mustafa Kumru, Mustafa Kocademir, Tayyibe Bardakci
Intermission
FC07
10:24 – 10:39
COMBINED COMPUTATIONAL AND EXPERIMENTAL STUDIES OF THE DUAL FLUORESCENCE IN DIMETHYLAMINOBENZONITRILE (DMABN), Anastasia Edsell, Steven Shipman
FC08
10:41 – 10:56
MODELING SPIN-ORBIT COUPLING IN THE HALOCARBENES , Phalgun Lolur, Richard Dawes, Scott Reid, Silver
Nyambo
FC09
10:58 – 11:13
GAS-PHASE CONFORMATIONS AND ENERGETICS OF PROTONATED 2′ -DEOXYADENOSINE-5′ MONOPHOSPHATE AND ADENOSINE-5′ -MONOPHOSPHATE: IRMPD ACTION SPECTROSCOPY AND THEORETICAL STUDIES, Ranran Wu, Y-W Nei, Chenchen He, Lucas Hamlow, Giel Berden, J. Oomens, M T Rodgers
36
FD. Atmospheric science
Friday, June 26, 2015 – 8:30 AM
Chair: Kyle N Crabtree, University of California, Davis, Davis, CA, USA
ar
y
FD01
8:30 – 8:45
OBSERVATION OF THE SIMPLEST CRIEGEE INTERMEDIATE CH2 OO IN THE GAS-PHASE OZONOLYSIS OF
ETHYLENE, Carrie Womack, Marie-Aline Martin-Drumel, Gordon G Brown, Robert W Field, Michael C McCarthy
FD02
8:47 – 9:02
HIGH-RESOLUTION SPECTRA OF CH2 OO : ASSIGNMENTS OF ν 5 AND 2ν 9 BANDS AND OVERLAPPED BANDS
OF ICH2 OO, Yu-Hsuan Huang, Li-Wei Chen, Yuan-Pern Lee
FD03
9:04 – 9:19
DIRECT INFRARED IDENTIFICATION OF THE CRIEGEE INTERMEDIATES syn- and anti-CH3 CHOO AND THEIR
DISTINCT CONFORMATION-DEPENDENT REACTIVITY, Hui-Yu Lin, Yu-Hsuan Huang, Xiaohong Wang, Joel Bowman, Yoshifumi Nishimura, Henry A Witek, Yuan-Pern Lee
in
FD04
9:21 – 9:36
THE Ã-X̃ ELECTRONIC TRANSITIONS OF THE CH2 BrOO AND CH2 ClOO RADICALS IN THE NEAR INFRARED
REGION, Neal Kline, Meng Huang, Terry A. Miller
FD05
9:38 – 9:53
THE Ã-X̃ ELECTRONIC TRANSITION OF CH2 IOO RADICAL IN THE NEAR INFRARED REGION, Neal Kline,
Meng Huang, Terry A. Miller, Phalgun Lolur, Richard Dawes
Pr
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FD06
9:55 – 10:10
A THEORETICAL CHARACTERIZATION OF ELECTRONIC STATES OF CH2 IOO AND CH2 OO RADICALS RELEVANT TO THE NEAR IR REGION , Richard Dawes, Phalgun Lolur, Meng Huang, Neal Kline, Terry A. Miller
Intermission
FD07
10:29 – 10:44
JET-COOLED LASER-INDUCED FLUORESCENCE SPECTROSCOPY OF T-BUTOXY, Neil J Reilly, Lan Cheng, John
F. Stanton, Terry A. Miller, Jinjun Liu
FD08
10:46 – 11:01
NITROSYL IODIDE, INO: MILLIMETER-WAVE SPECTROSCOPY GUIDED BY AB IN IT IO QUANTUM CHEMICAL COMPUTATION, Stephane Bailleux, Denis Duflot, Shohei Aiba, Hiroyuki Ozeki
FD09
11:03 – 11:18
DISPERSED FLUORESCENCE SPECTROSCOPY OF JET-COOLED ISOBUTOXY, 2-METHYL-1-BUTOXY, AND
ISOPENTOXY RADICALS , Md Asmaul Reza, Neil J Reilly, Jahangir Alam, Amy Mason, Jinjun Liu
FD10
11:20 – 11:35
PHOTODISSOCIATION OF METHYL ISOTHIOCYANATE STUDIED USING CHIRPED PULSE UNIFORM FLOW
SPECTROSCOPY, Nuwandi M Ariyasingha, Lindsay N. Zack, Chamara Abeysekera, Baptiste Joalland, Arthur Suits
FD11
11:37 – 11:52
DISPERSED FLUORESCENCE SPECTROSCOPY OF JET-COOLED METHYLCYCLOHEXOXY RADICALS ,
Jahangir Alam, Md Asmaul Reza, Amy Mason, Jinjun Liu
FE. Small molecules
37
Friday, June 26, 2015 – 8:30 AM
Chair: Robert W Field, MIT, Cambridge, MA, USA
ar
y
FE01
8:30 – 8:45
TOWARDS A GLOBAL FIT OF THE COMBINED MILLIMETER-WAVE AND HIGH RESOLUTION FTIR DATA FOR
THE LOWEST EIGHT VIBRATIONAL STATES OF HYDRAZOIC ACID (HN3 ) , Brent K. Amberger, R. Claude Woods,
Brian J. Esselman, Robert J. McMahon
FE02
8:47 – 9:02
MILLIMETER-WAVE SPECTROSCOPY AND GLOBAL ANALYSIS OF THE LOWEST EIGHT VIBRATIONAL
STATES OF DEUTERATED HYDRAZOIC ACID (DN3 ), Brent K. Amberger, R. Claude Woods, Brian J. Esselman, Robert
J. McMahon
FE03
9:04 – 9:19
SIMPLIFIED CARTESIAN BASIS MODEL FOR INTRAPOLYAD EMISSION INTENSITIES IN THE Ã → X̃ BENTTO-LINEAR TRANSITION OF ACETYLENE, Barratt Park, Adam H. Steeves, Joshua H Baraban, Robert W Field
in
FE04
9:21 – 9:36
OBSERVATION OF LEVEL-SPECIFIC PREDISSOCIATION RATES IN S1 ACETYLENE, Catherine A. Saladrigas, Jun
Jiang, Robert W Field
FE05
9:38 – 9:53
FULL DIMENSIONAL ROVIBRATIONAL VARIATIONAL CALCULATIONS OF THE S1 STATE OF C2 H2 ,
Bryan Changala, Joshua H Baraban, John F. Stanton
Pr
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im
Intermission
FE06
10:12 – 10:27
MILLIMETER-WAVE SPECTROSCOPY OF FORMYL AZIDE (HC(O)N3 ), Nicholas A. Walters, Brent K. Amberger,
Brian J. Esselman, R. Claude Woods, Robert J. McMahon
FE07
10:29 – 10:44
MILLIMETER-WAVE ROTATIONAL SPECTRUM OF DEUTERATED NITRIC ACID, Rebecca A.H. Butler, Camren
Coplan, Doug Petkie, Ivan Medvedev, Frank C. De Lucia
FE08
10:46 – 11:01
THEORETICAL ANALYSIS OF THE RESONANCE FOUR-WAVE MIXING AMPLITUDES: A FULLY NONDEGENERATE CASE., Alexander Kouzov
FE09
11:03 – 11:18
SAND IN THE LABORATORY. PRODUCTION AND INTERROGATION OF GAS PHASE SILICATES.,
Damian L Kokkin, Timothy Steimle
FE10
11:20 – 11:35
IMPACT OF COMPLEX-VALUED ENERGY FUNCTION SINGULARITIES ON THE BEHAVIOUR OF RAYLEIGHSCHRÖDINGER PERTURBATION SERIES. H2 CO MOLECULE VIBRATIONAL ENERGY SPECTRUM.,
Andrey Duchko, Alexandr Bykov
38
MA. Plenary
Monday, June 22, 2015 – 8:30 AM
ar
y
Chair: Gregory S. Girolami, University of Illinois at Urbana-Champaign, Urbana, IL, USA
Welcome
Phyllis M. Wise, Chancellor
University of Illinois at Urbana-Champaign
8:30
in
MA01
8:40 – 9:20
BREATHING EASIER THROUGH SPECTROSCOPY: STUDYING FREE RADICAL REACTIONS IN AIR POLLUTION
CHEMISTRY
MITCHIO OKUMURAa , Division of Chemistry and Chemical Engineering, California Institute of Technology,
Pasadena, CA, USA.
Pr
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Air pollution arises from the oxidation of volatile organic compounds emitted into the atmosphere from both anthropogenic and biogenic sources. Free radicals dominate the gas phase chemistry leading to the formation of tropospheric ozone,
oxygenated organic molecules and organic aerosols, but this chemistry is complex. In this presentation, advances in our
understanding of the spectroscopy and chemistry of atmospheric free radicals will be described that have come from exploiting the sensitivity and specificity of methods such as Cavity Ringdown Spectroscopy, Multiplexed Photoionization Mass
Spectrometry and Cavity-Enhanced Frequency Comb Spectroscopy.
a
This work was supported by the National Science Foundation and the National Aeronautics and Space Administration.
MA02
MOLECULAR ROTATION SIGNALS: MOLECULE CHEMISTRY AND PARTICLE PHYSICS
9:25 – 10:05
JENS-UWE GRABOW, Institut für Physikalische Chemie und Elektrochemie, Gottfried-Wilhelm-LeibnizUniversität, Hannover, Germany.
Molecules - large or small - are attractive academic resources, with numerous questions on their chemical behaviour as
well as problems in fundamental physics now (or still) waiting to be answered: Targeted by high-resolution spectroscopy, a
rotating molecular top can turn into a laboratory for molecule chemistry or a laboratory for particle physics.
Once successfully entrained (many species - depending on size and chemical composition - have insufficient vapour
pressures or are of transient nature, such that specifically designed pulsed-jet sources are required for their transfer into
the gas phase or in-situ generation) into the collision-free environment of a supersonic-jet expansion, each molecular top
comes with its own set of challenges, theoretically and experimentally: Multiple internal interactions are causing complicated
energy level schemes and the resulting spectra will be rather difficult to predict theoretically. Experimentally, these spectra are
difficult to assess and assign. With today’s broad-banded chirp microwave techniques, finding and identifying such spectral
features have lost their major drawback of being very time consuming for many molecules. For other molecules, the unrivalled
resolution and sensitivity of the narrow-banded impulse microwave techniques provide a window to tackle - at the highest
precision available to date – fundamental questions in physics, even particle physics – potentially beyond the standard model.
Molecular charge distribution, properties of the chemical bond, details on internal dynamics and intermolecular interaction, the (stereo-chemical) molecular structure (including the possibility of their spatial separation) as well as potential
evidence for tiny yet significant interactions encode their signature in pure molecular rotation subjected to time-domain microwave spectroscopic techniques. Ongoing exciting technical developments promise rapid progress. We present recent
examples from Hannover, new directions, and an outlook at the future of molecular rotation spectroscopy.
Intermission
39
MA03
10:35 – 11:15
IT IS WATER WHAT MATTERS: THz SPECTROSCOPY AS A TOOL TO STUDY HYDRATION DYNAMICS
MARTINA HAVENITH, Physikalische Chemie II, Ruhr University Bochum, Bochum, Germany.
ar
y
Terahertz absorption spectroscopy has turned out to be a new powerful tool to study biomolecular hydration. The development of THz technology helped to fill the experimental gap in this frequency range. These experimental advances had to
go hand in hand with the development of theoretical concepts that have been developed in the recent years to describe the
underlying solute-induced sub-picosecond dynamics of the hydration shell. This frequency range covers the rattling modes
of the ion with its hydration cage and allowed to derive major conclusions on the molecular picture of ion hydration, a key
issue in chemistry. By a combination of experiment and theory it is now possible to rigorously dissect the THz spectrum of a
solvated biomolecule into the distinct solute, solvent and solute-solvent coupled contributions Moreover, we highlight recent
results that show the significance of hydrogen bond dynamics for molecular recognition. In all of these examples, a gradient
of water motion toward functional sites of proteins is observed, the so-called hydration funnel. The efficiency of the coupling
at THz frequencies is explained in terms of a two-tier (short- and long-range) solute-solvent interaction.
in
MA04
11:20 – 12:00
CPUF: CHIRPED-PULSE MICROWAVE SPECTROSCOPY IN PULSED UNIFORM SUPERSONIC FLOWS
Pr
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ARTHUR SUITS, CHAMARA ABEYSEKERA, LINDSAY N. ZACK, BAPTISTE JOALLAND, NUWANDI
M ARIYASINGHA, Department of Chemistry, Wayne State University, Detroit, MI, USA; BARRATT PARK,
ROBERT W FIELD, Department of Chemistry, MIT, Cambridge, MA, USA; IAN SIMS, Institut de Physique de
Rennes, Université de Rennes 1, Rennes, France.
Chirped-pulse Fourier-transform microwave spectroscopy has stimulated a resurgence of interest in rotational spectroscopy owing to the dramatic reduction in spectral acquisition time it enjoys when compared to cavity-based instruments.
This suggests that it might be possible to adapt the method to study chemical reaction dynamics and even chemical kinetics
using rotational spectroscopy. The great advantage of this would be clear, quantifiable spectroscopic signatures for polyatomic
products as well as the possibility to identify and characterize new radical reaction products and transient intermediates. To
achieve this, however, several conditions must be met: 1) products must be thermalized at low temperature to maximize the
population difference needed to achieve adequate signal levels and to permit product quantification based on the rotational
line strength; 2) a large density and volume of reaction products is also needed to achieve adequate signal levels; and 3) for
kinetics studies, a uniform density and temperature is needed throughout the course of the reaction. These conditions are
all happily met by the uniform supersonic flow produced from a Laval nozzle expansion. In collaboration with the Field
group at MIT we have developed a new instrument we term a CPUF (Chirped-pulse/Uniform Flow) spectrometer in which
we can study reaction dynamics, photochemistry and kinetics using broadband microwave and millimeter wave spectroscopy
as a product probe. We will illustrate the performance of the system with a few examples of photodissociation and reaction
dynamics, and also discuss a number of challenges unique to the application of chirped-pulse microwave spectroscopy in the
collisional environment of the flow. Future directions and opportunities for application of CPUF will also be explored.
40
MF. Mini-symposium: High-Precision Spectroscopy
Monday, June 22, 2015 – 1:30 PM
Chair: Michael Heaven, Emory University, Atlanta, GA, USA
Journal of Molecular Spectroscopy Review Lecture
1:30 – 2:00
ar
y
MF01
PHYSICS BEYOND THE STANDARD MODEL FROM MOLECULAR HYDROGEN SPECTROSCOPY
WIM UBACHS, EDCEL JOHN SALUMBIDES, JULIJA BAGDONAITE, Department of Physics and Astronomy, VU University , Amsterdam, Netherlands.
Pr
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in
The spectrum of molecular hydrogen can be measured in the laboratory to very high precision using advanced laser and
molecular beam techniques, as well as frequency-comb based calibration [1,2]. The quantum level structure of this smallest
neutral molecule can now be calculated to very high precision, based on a very accurate (10−15 precision) Born-Oppenheimer
potential [3] and including subtle non-adiabatic, relativistic and quantum electrodynamic effects [4]. Comparison between
theory and experiment yields a test of QED, and in fact of the Standard Model of Physics, since the weak, strong and gravitational forces have a negligible effect. Even fifth forces beyond the Standard Model can be searched for [5]. Astronomical
observation of molecular hydrogen spectra, using the largest telescopes on Earth and in space, may reveal possible variations
of fundamental constants on a cosmological time scale [6]. A study has been performed at a ’look-back’ time of 12.5 billion years [7]. In addition the possible dependence of a fundamental constant on a gravitational field has been investigated
from observation of molecular hydrogen in the photospheres of white dwarfs [8]. The latter involves a test of the Einsteins
equivalence principle.
[1] E.J. Salumbides et al., Phys. Rev. Lett. 107, 143005 (2011).
[2] G. Dickenson et al., Phys. Rev. Lett. 110, 193601 (2013).
[3] K. Pachucki, Phys. Rev. A82, 032509 (2010).
[4] J. Komasa et al., J. Chem. Theory Comp. 7, 3105 (2011).
[5] E.J. Salumbides et al., Phys. Rev. D87, 112008 (2013).
[6] F. van Weerdenburg et al., Phys. Rev. Lett. 106, 180802 (2011).
[7] J. Badonaite et al., Phys. Rev. Lett. 114, 071301 (2015).
[8] J. Bagdonaite et al., Phys. Rev. Lett. 113, 123002 (2014).
MF02
PRECISION SPECTROSCOPY ON HIGHLY-EXCITED VIBRATIONAL LEVELS OF H2
2:05 – 2:20
MING LI NIU, EDCEL JOHN SALUMBIDES, WIM UBACHS, Department of Physics and Astronomy, VU
University , Amsterdam, Netherlands.
The ground electronic energy levels of H2 have been used as a benchmark system for the most precise comparisons
between ab initio calculations and experimental investigations. Recent examples include the determinations of the ionization
energy [1], fundamental vibrational energy splitting [2], and rotational energy progression extending to J = 16 [3]. In general,
the experimental and theoretical values are in excellent agreement with each other. The energy calculations, however, reduce
in accuracy with the increase in rotational and vibrational excitation, limited by the accuracy of non-Born Oppenheimer
corrections, as well as the higher-order QED effects. While on the experimental side, it remains difficult to sufficiently
populate these excited levels in the ground electronic state.
We present here our high-resolution spectroscopic study on the X 1 Σ+
g electronic ground state levels with very high
vibrational quanta (ν = 10, 11, 12). Vibrationally-excited H2 are produced from the photodissociation of H2 S [4], and
subsequently probed by a narrowband pulsed dye laser system. The experimental results are consistent with and more accurate
than the best theoretical values [5]. These vibrationally-excited level energies are also of interest to studies that extract
constraints on the possible new interactions that extend beyond the Standard Model [6].
[1] J. Liu et al., J. Chem. Phys. 130, 174306 (2009).
[3] E.J. Salumbides et al., Phys. Rev. Lett. 107, 143005 (2011).
[4] J. Steadman and T. Baer, J. Chem. Phys. 91, 6113 (1989).
[5] J. Komasa et al., J. Chem. Theory Comp. 7, 3105 (2011).
[6] E.J. Salumbides et al., Phys. Rev. D 87, 112008 (2013).
41
MF03
2:22 – 2:37
BOUNDS ON THE NUMBER AND SIZE OF EXTRA DIMENSIONS FROM MOLECULAR SPECTROSCOPY
ar
y
EDCEL JOHN SALUMBIDES, Department of Physics and Astronomy, VU University , Amsterdam, Netherlands; BERT SCHELLEKENS, Theoretical Physics, Nikhef, Amsterdam, Netherlands; BEATRIZ GATORIVERA, Instituto de Fisica Fundamental, CSIC, Madrid, Spain; WIM UBACHS, Department of Physics and
Astronomy, VU University , Amsterdam, Netherlands.
Pr
el
im
in
Modern string theories, which seek to produce a consistent description of physics beyond the Standard Model that also
includes the gravitational interaction, appear to be most consistent if a large number of dimensions are postulated. For
example the mysterious M-theory, which generalizes all consistent versions of superstring theories, require 11 dimensions. We
demonstrate that investigations of quantum level energies in simple molecular systems provide a testing ground to constrain
the size of compactified extra dimensions, for example those proposed in the ADD [1] and RS scenarios [2]. This is made
possible by the recent progress in precision metrology with ultrastable lasers on energy levels in neutral molecular hydrogen
+
+
(H2 , HD and D2 ) [3] and the molecular hydrogen ions (H+
2 , HD and D2 ) [4]. Comparisons between experiment and quantum
electrodynamics calculations for these molecular systems can be interpreted in terms of probing large extra dimensions, under
which conditions gravity will become much stronger. Molecules are a probe of space-time geometry at typical distances where
chemical bonds are effective, i.e. at length scales of an Å.
[1] N. Arkani-Hamed, S. Dimopoulos and G. Dvali, Phys. Lett. B 429, 263 (1998)
[2] L. Randall and R. Sundrum, Phys. Rev. Lett. 83, 3370 (1999).
[4] J. C. J. Koelemeij et al., Phys. Rev. Lett. 98, 173002 (2007).
MF04
2:39 – 2:54
CONTINUOUS SUPERSONIC EXPANSION DISCHARGE SOURCE FOR HIGH-PRECISION MID-INFRARED SPECTROSCOPY OF COLD MOLECULAR IONS
COURTNEY TALICSKA, MICHAEL PORAMBO, Department of Chemistry, University of Illinois at UrbanaChampaign, Urbana, IL, USA; BENJAMIN J. McCALL, Departments of Chemistry and Astronomy, University
of Illinois at Urbana-Champaign, Urbana, IL, USA.
The low temperatures and pressures of the interstellar medium provide an ideal environment for gas phase ion-neutral
reactions that play an essential role in the chemistry of the universe. High-precision laboratory spectra of molecular ions
are necessary to facilitate new astronomical discoveries and provide a deeper understanding of interstellar chemistry, but
forming ions in measurable quantities in the laboratory has proved challenging. Even when cryogenically cooled, the high
temperatures and pressures of typical discharge cells lead to diluted and congested spectra from which extracting chemical
information is difficult. Here we overcome this challenge by coupling an electric discharge to a continuous supersonic
expansion source to form ions cooled to low temperatures. The ion production abilities of the source have been demonstrated
previously as ion densities on the order of 1010 -1012 cm−3 have been observed for H3 + .a With a smaller rotational constant
and the expectation that it will be formed with comparable densities, HN2 + is used as a reliable measure of the cooling
abilities of the source. Ions are probed through the use of a widely tunable mid-infrared (3-5 µm) spectrometer based on light
formed by difference frequency generation and noise-immune cavity-enhanced optical heterodyne molecular spectroscopy
(NICE-OHMS).b To improve the sensitivity of the instrument the discharge is electrically modulated and the signal is fed into
a lock-in amplifier before being recorded by a custom data acquisition program. Rovibrational transitions of H3 + and HN2 +
have been recorded, giving rotational temperatures of 80-120 K and 35-40 K, respectively. With verification that the source
is producing rotationally cold ions, we move toward the study of primary ions of more astronomical significance, including
H2 CO+ .
a
K. N. Crabtree, C. A. Kaufman, and B. J. McCall, Rev. Sci. Instrum. 81, 086103 (2010).
b
M. W. Porambo, B. M. Siller, J. M. Pearson, and B. J. McCall, Opt. Lett. 37, 4422 (2012)
42
MF05
2:56 – 3:11
PROGRESS TOWARDS A HIGH-PRECISION INFRARED SPECTROSCOPIC SURVEY OF THE
H+
3
ION
ar
y
ADAM J. PERRY, JAMES N. HODGES, CHARLES R. MARKUS, G. STEPHEN KOCHERIL, PAUL A.
JENKINS II, Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL, USA; BENJAMIN J. McCALL, Departments of Chemistry and Astronomy, University of Illinois at Urbana-Champaign,
Urbana, IL, USA.
a
O. Polyansky, et al., Phil. Trans. R. Soc. A (2012), 370, 5014.
M. Pavanello, et al., J. Chem. Phys. (2012), 136, 184303.
c
L. Diniz, et al., Phys. Rev. A (2013), 88, 032506.
d
L. Lodi, et al., Phys. Rev. A (2014), 89, 032505.
e
J. Hodges, et al., J. Chem. Phys (2013), 139, 164201.
Pr
el
im
b
in
The trihydrogen cation, H+
3 , represents one of the most important and fundamental molecular systems. Having only
two electrons and three nuclei, H+
3 is the simplest polyatomic system and is a key testing ground for the development of
new techniques for calculating potential energy surfaces and predicting molecular spectra. Corrections that go beyond the
Born-Oppenheimer approximation, including adiabatic, non-adiabatic, relativistic, and quantum electrodynamic corrections
are becoming more feasible to calculateabcd . As a result, experimental measurements performed on the H+
3 ion serve as
important benchmarks which are used to test the predictive power of new computational methods.
By measuring many infrared transitions with precision at the sub-MHz level it is possible to construct a list of the most
highly precise experimental rovibrational energy levels for this molecule. Until recently, only a select handful of infrared
transitions of this molecule have been measured with high precision (∼ 1 MHz)e . Using the technique of Noise Immune
Cavity Enhanced Optical Heterodyne Velocity Modulation Spectroscopy, we are aiming to produce the largest high-precision
spectroscopic dataset for this molecule to date. Presented here are the current results from our survey along with a discussion
of the combination differences analysis used to extract the experimentally determined rovibrational energy levels.
Intermission
MF06
3:30 – 3:45
+
HIGH PRECISION INFRARED SPECTROSCOPY OF OH
CHARLES R. MARKUS, ADAM J. PERRY, JAMES N. HODGES, G. STEPHEN KOCHERIL, PAUL A.
JENKINS II, Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL, USA; BENJAMIN J. McCALL, Departments of Chemistry and Astronomy, University of Illinois at Urbana-Champaign,
Urbana, IL, USA.
The molecular ion OH+ is of significant importance to interstellar chemistry. OH+ is a key intermediate in the formation
of water, and the ratios of OH+ to H2 O+ and H3 O+ have been used to calculate the cosmic ray ionization rates in diffuse
molecular clouds.abc To improve on previous spectroscopic work, the sensitive technique Noise Immune Cavity Enhanced
Optical Heterodyne Velocity Modulation Spectroscopy (NICE-OHVMS) has been used to record rovibrational transitions of
+
+ de
Using an optical frequency
OH+ . Previously this approach has been used to investigate HCO+ , H+
3 , CH5 , and HeH .
comb for precise frequency calibration, the OH+ line centers have been determined with ∼MHz uncertainties. Here the
most precise and accurate list of rovibrational transitions of OH+ is presented. These values can then be used to empirically
determine rotational transitions through combination difference analysis.
a
F. Wyrowski et al., Astron. Astrophys., (2010),26,5.
E. González-Alfonso et al., Astron. Astrophys., (2013), 550, A25.
c
N. Indriolo et al., Astrophys. J., (2015), 800, 40.
d
J.N. Hodges et al., Chem. Phys., (2013), 139, 164201.
e
A.J. Perry et al., J. Chem. Phys., (2014), 141, 101101.
b
43
MF07
TOWARD TWO-COLOR SUB-DOPPLER SATURATION RECOVERY KINETICS IN CN (X, v = 0, J)
3:47 – 4:02
ar
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HONG XU, DAMIEN FORTHOMME, Department of Chemistry, Brookhaven National Laboratory, Upton, NY,
USA; TREVOR SEARSa , GREGORY HALL, Chemistry Department, Brookhaven National Laboratory, Upton,
NY, USA; PAUL DAGDIGIAN, Department of Chemistry, Johns Hopkins University, Baltimore, MD, USA.
also: Chemistry Department, Stony Brook University, Stony Brook, NY 11794-3400
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Collision-induced rotational energy transfer among rotational levels of ground state CN (X 2 Σ+ , v = 0) radicals has been
probed by saturation recovery experiments, using high-resolution, polarized transient FM spectroscopy to probe the recovery
of population and the decay of alignment following ns pulsed laser depletion of selected CN rotational levels. Despite the
lack of Doppler selection in the pulsed depletion and the thermal distribution of collision velocities, the recovery kinetics are
found to depend on the probed Doppler shift of the depleted signal. The observed Doppler-shift-dependent recovery rates
are a measure of the velocity dependence of the inelastic cross sections, combined with the moderating effects of velocitychanging elastic collisions. New experiments are underway, in which the pulsed saturation is performed with sub-Doppler
velocity selection. The time evolution of the spectral hole bleached in the initially thermal CN absorption spectrum can
characterize speed-dependent inelastic collisions along with competing elastic velocity-changing collisions, all as a function
of the initially bleached velocity group and rotational state. The initial time evolution of the depletion recovery spectrum
can be compared to a stochastic model, using differential cross sections for elastic scattering as well as speed-dependent total
inelastic cross sections, derived from ab initio scattering calculations. Progress to date will be reported.
Acknowledgments: Work at Brookhaven National Laboratory was carried out under Contract No. DE-AC02-98CH10886
and DE-SC0012704 with the U.S. Department of Energy and supported by its Office of Basic Energy Sciences, Division of
Chemical Sciences, Geosciences and Biosciences.
MF08
4:04 – 4:19
AN EMPIRICAL DIPOLE POLARIZABILITY FOR He FROM A FIT TO SPECTROSCOPIC DATA YIELDING ANALYTIC EMPIRICAL POTENTIALS FOR ALL ISOTOPOLOGUES OF HeH+
YOUNG-SANG CHO, ROBERT J. LE ROY, Department of Chemistry, University of Waterloo, Waterloo, ON,
Canada; NIKESH S. DATTANIa , Graduate School of Science, Department of Chemistry, Kyoto University,
Kyoto, Japan.
All available spectroscopic data for all stable isotopologues of HeH+ are analyzed with a direct-potential-fit (DPF)
procedure that uses least-squares fits to experimental data in order to optimize the parameters defining an analytic potential.
Since the coefficient of the leading (1/r4 ) inverse-power term is C4 = αHe /2, when treated as a free parameter in the fit,
it provides an independent empirical estimate of the polarizability of the He atom. The fact that the present model for the
long-range behaviour includes accurate theoretical C6 , C7 and C8 coefficients (which are held fixed in the fits) should make
it possible to obtain a good estimate of this quantity.
The Boltzmann constant kB , a fundamental³constant
´ that can define temperature, is directly related to the dipole polarizp
+2
ability α of a gas by the expression kB = 3ǫα0 ǫǫrr −1
T , in which ǫ0 is the permitivity of free space, and ǫr is the relative
dielectric permitivity at pressure p and temperature T . If kB can be determined with greater precision, it can be used to define
temperature based on a fundamental constant, rather than based on the rather arbitrary triple point of water, which is only
known to 5 digits of precision. α for He is known theoretically to 8 digits of precision, but an empirical value lags behind.
This work, examines the question of how precisely αHe can be determined from a DPF to spectroscopic HeH+ data, where
the limiting long-range tail of the analytic potential has the correct form implied by Rydberg theory: αHe /2r4 . Although the
highest observed vibrational level is bound by over 1000 cm−1 , our current fits determine an empirical C4 = αHe /2 with
an uncertainty of only 0.6%. It has been shown that with more precise spectroscopic data near the dissociation, αHe can be
determined with high enough precision to determine a more precise kB and hence redefine temperature more accuratelyb .
a
b
[email protected]
Dattani N S. & Puchalski M. (2015) Physical Review Letters (in press)
44
MF09
4:21 – 4:36
+
+
+
ANALYTIC EMPIRICAL POTENTIALS FOR BeH , BeD , AND BeT INCLUDING UP TO 4TH ORDER QED IN
THE LONG-RANGE, AND PREDICTIONS FOR THE HALO NUCLEONIC MOLECULES 11 BeH+ and 14 BeH+ .
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LENA C. M. LI CHUN FONG, Department of Chemistry, University of Waterloo, Waterloo, ON, Canada;
GRZEGORZ LACH, International Institute of Molecular and Cell Biology, Warsaw, Poland; ROBERT J. LE
ROY, Department of Chemistry, University of Waterloo, Waterloo, ON, Canada; NIKESH S. DATTANIa , Graduate School of Science, Department of Chemistry, Kyoto University, Kyoto, Japan.
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The 13.81(8)s half-life of the halo nucleonic atom 11 Be is orders of magnitude longer than those for any other halo
nucleonic atom known, and makes Be-based diatomics the most promising candidates for the formation of the first halo
nucleonic molecules. However, the 4e− species LiH and BeH+ are some of the first molecules for which the highest accuracy
ab initio methods are not accessible, so empirical potential energy functions will be important for making predictions and
for benchmarking how ab initio calculations break down at this transition from 3e− to 4e− . BeH+ is also very light, and has
one of the most extensive data sets involving a tritium isotopologue, making it a very useful benchmark for studying BornOppenheimer breakdown. We therefore seek to determine an empirical analytic potential energy function for BeH+ that has
as much precision as possible. To this end, all available spectroscopic data for all stable isotopologues of BeH+ are analyzed
in a standard direct-potential-fit procedure that uses least-squares fits to optimize the parameters defining an analytic potential.
The “Morse/Long-range” (MLR) model used for the potential energy function incorporates the inverse-power long-range tail
required by theory, and the calculation of the leading long-range coefficients C4 , C6 , C7 , and C8 include non-adiabatic terms,
and up to 4th order QED corrections. As a by-product, we have calculated some fundamental properties of 1e− systems with
unprecedented precision, such as the dipole, quadrupole, octupole, non-adiabatic, and mixed higher order polarizabilities of
hydrogen, deuterium, and tritium. We provide good first estimates for the transition energies for the halo nucleonic species
11
BeH+ and 14 BeH+ .
a
[email protected]
MF10
4:38 – 4:53
ANALYTIC EMPIRICAL POTENTIAL AND ITS COMPARISON TO STATE OF THE ART ab initio CALCULATIONS
FOR THE 6e− EXCITED b(13 Πu )-STATE OF Li2 .
NIKESH S. DATTANI, Graduate School of Science, Kyoto University, Kyoto, Japan; ROBERT J. LE ROY,
Department of Chemistry, University of Waterloo, Waterloo, ON, Canada.
Despite only having 6e− , the most sophisticated Li2 (b, 13 Πu ) calculationa has an re that disagrees with the empirical
value by over 1500% of the latter’s uncertainty, and energy spacings that disagree with those of the empirical potential by
up to over 1.5cm−1 . The discrepancy here is far more than for the ground state of the 5e− system BeH, for which the best
ab initio calculation gives an re which disagrees with the empirical value by less than 200% of the latter’s uncertaintyb . In
addition to this discrepancy, other reasons motivating the construction of an analytic empirical potential for Li2 (b, 13 Πu )
include (1) the fact that it is the most deeply bound Li2 state, (2) it is the only Li2 state out of the lowest five, for which no
analytic empirical potential has yet been built, (3) the state it mixes with, the A(11 Σu )-state, is one of the most thoroughly
characterized molecular states, but has a small gap of missing data in part of the region where it mixes with the b-state, and
(4) it is one of the states accessible by new ultra-high precision techniques based on photoassociationc,d . Finally (5) there is
currently a discrepancy between the most sophisticated 3e− ab initio calculatione , and the most current empirical valuef , for
the first Li(2 S)−Li(2 P ) interaction term (C3 ), despite the latter being the most precise experimentally determined oscillator
strength for any system, by an order of magnitudee . The b-state is one of the states that has this exact C3 interaction term.
a
Musial & Kucharski (2014) J. Chem. Theor. Comp. 10, 1200.
Dattani N. S. (2015) J. Mol. Spec. http://dx.doi.org/10.1016/j.jms.2014.09.005
c
Semczuk M., Li X., Gunton W., Haw M., Dattani N. S., Witz J., Mills A., Jones D. J., Madison K. W. (2013) Phys. Rev. A 87, 052505
d
Gunton W., Semczuk M., Dattani N. S., Madison K. W. (2013) Phys. Rev. A 88, 062510
e
Tang L.-Y., Yan Z.-C., Shi T.-Y., Mitroy J (2011) Phys. Rev. A 84, 052502.
f
Le Roy R. J., Dattani N. S., Coxon J. A., Ross A. J., Crozet P., Linton C. (2009) J. Chem Phys. 131, 204309
b
45
MF11
4:55 – 5:10
+
PRECISION SPECTROSCOPY OF TRAPPED HfF WITH A COHERENCE TIME OF 1 SECOND
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KEVIN COSSEL, WILLIAM CAIRNCROSS, MATT GRAU, DAN GRESH, YAN ZHOU, JUN YE, ERIC
CORNELL, JILA, National Institute of Standards and Technology and Univ. of Colorado Department of Physics,
University of Colorado, Boulder, Boulder, CO, USA.
Trapped molecular ions provide new systems for precision spectroscopy and tests of fundamental physics. For example,
measurements of the permanent electric dipole moment of the electron (eEDM) test time-reversal symmetrya . Currently, we
are using Ramsey spectroscopy between spin states of the metastable 3 ∆1 state in trapped HfF+ for a measurement of the
eEDMb,c . We are regularly performing spectroscopy with a Ramsey time of 500 ms yielding what, to our knowledge, is the
narrowest spectral line observed in a molecular system. Here, we will provide an overview of the experiment and the current
eEDM results.
a
The ACME Collaboration, et al., Science 343, 269 (2014)
H. Loh, K. C. Cossel, M. C. Grau, K.-K. Ni, E. R. Meyer, J. L. Bohn, J. Ye, E. A. Cornell, Science 342, 1220 (2013).
c
A. E. Leanhardt, J. L. Bohn, H. Loh, M. C. Grau, P. Maletinski, E. R. Meyer, L. C. Sinclair, R. P. Stutz, E. A. Cornell, J. Mol. Spec. 270, 1 (2011).
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MF12
5:12 – 5:27
BROADBAND FREQUENCY COMB AND CW-LASER VELOCITY MODULATION SPECTROSCOPY OF ThF+
DAN GRESH, KEVIN COSSEL, JUN YE, ERIC CORNELL, JILA, National Institute of Standards and Technology and Univ. of Colorado Department of Physics, University of Colorado, Boulder, CO, USA.
An experimental search for the permanent electric dipole moment of the electron (eEDM) is currently being performed
using the metastable 3 ∆1 state in trapped HfF+ (a) . The use of ThF+ could significantly increase the sensitivity due to
the larger effective electric field and longer 3 ∆1 state lifetime. Previous work by the Heaven group has identified several
low-lying ThF+ electronic statesb ; however, the ground state could not be conclusively assigned. In addition, transitions to
intermediate electronic states have not been identified, but they are necessary for state detection, manipulation, and readout
in an eEDM experiment. To date we have acquired 3700 cm−1 of densely-sampled ThF+ spectra in the 695 – 1020 nm region
with frequency combc and cw-laser velocity modulation spectroscopyd . With high resolution, we have accurately fit more
than 20 ThF+ vibronic transitions, including electronic states spaced by the known X-a energy separationb . We will report on
the ThF+ ground state assignment and its implications for an eEDM experiment.
a
H. Loh, K. C. Cossel, M. C. Grau, K.-K. Ni, E. R. Meyer, J. L. Bohn, J. Ye, E. A. Cornell, Science 342, 1220 (2013).
B. J. Barker, I. O. Antonov, M. C. Heaven, K. A. Peterson, J. Chem. Phys. 136, 104305 (2012).
c
L. C. Sinclair, K. C. Cossel, T. Coffey, J. Ye, E. A. Cornell, PRL 107, 093002 (2011).
d
K.C. Cossel et. al., Chem. Phys. Lett. 546, 1 (2012).
b
46
MF13
5:29 – 5:44
PURE MW DATA FOR v = 0 − 6 OF PbI GIVE VIBRATIONAL SPACINGS AND A FULL ANALYTIC POTENTIAL
ENERGY FUNCTION
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JI HO (CHRIS) YOO, Department of Chemistry, University of Waterloo, Waterloo, ON, Canada; COREY
EVANS, Department of Chemistry, University of Leicester, Leicester, United Kingdom; NICK WALKER, School
of Chemistry, Newcastle University, Newcastle-upon-Tyne, United Kingdom; ROBERT J. LE ROY, Department
of Chemistry, University of Waterloo, Waterloo, ON, Canada.
in
At last year’s ISMS meeting, Zaleski et al. reported new broadband MW spectroscopy measurements of pure rotational
transitions in the v = 0 − 6 levels of the 2 Π1/2 ground electronic state of PbI.a The analysis presented at that time was a
conventional v-level by v-level ‘band-constant’ analysis performed using the PGopher program.b That level-by-level PGopher
analysis yielded values of Bv , Dv and five spin-splitting parameters for each vibrational level of each isotopologue. Ignoring
the spin-splitting information, the Bv and Dv values were used to generate a set of synthetic pure R(0) transitions for each
level that were taken to represent the “mechanical” information about the molecule contained in these spectra. A standard
direct-potential-fit (DPF) analysisc was then used to fit these data to an “Expanded Morse Oscillator” (EMO) potential function
form. The well-depth parameter De was fixed at the literature value, while values of the equilibrium distance re and three
EMO exponent-coefficient expansion ‘potential shape’ parameters are determined from the fits. The best fits to the data
yield potentials whose fundamental vibrational spacings are in excellent agreement with experimentd together with reliable
predictions for the first five overtone energies.
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a
D.P. Zaleski, H. Köckert, S.L. Stephens, N. Walker, L.-M. Dickens, and C. Evans, paper RE08 at the 69th International Symposium on Molecular Spectroscopy, University
of Illinois (2014).
b
PGopher - a Program for Simulating Rotational Structure, C. M. Western, University of Bristol, http://pgopher.chm.bris.ac.uk
c
DPotFit 2.0: A Computer Program for fitting Diatomic Molecule Spectra to Potential Energy Functions, R.J. Le Roy, J. Seto and Y. Huang, University of Waterloo Chemical
Physics Research Report CP-667 (2013); see http://leroy.uwaterloo.ca/programs/.
d
K. Ziebarth, R. Breidohr, O. Shestakov and E.H. Fink, Chem. Phys. Lett. 190, 271 (1992).
47
MG. Structure determination
Monday, June 22, 2015 – 1:30 PM
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Chair: Ha Vinh Lam Nguyen, Université Paris-Est Créteil, Créteil, France
MG01
DETECTION OF HSNO, A CRUCIAL INTERMEDIATE LINKING NO AND H2 S CHEMISTRIES
1:30 – 1:45
in
MARIE-ALINE MARTIN-DRUMEL, Spectroscopy Lab, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA; CARRIE WOMACK, Department of Chemistry, MIT, Cambridge, MA, USA; KYLE N CRABTREE, Department of Chemistry, The University of California, Davis, CA, USA; SVEN THORWIRTH, I.
Physikalisches Institut, Universität zu Köln, Köln, Germany; MICHAEL C McCARTHY, Atomic and Molecular Physics, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA.
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The simplest S-nitrosothiol, thionitrous acid (HSNO), is a reactive molecule of both biological and astronomical interest.
Here we report the first detection of both cis- and trans-HSNO by means of Fourier-transform microwave spectroscopy and
double resonance experiments. Surprisingly, HSNO is readily produced in a gas expansion of H2 S and NO, i.e. without
applying any discharge. Once formed, HSNO appears quite stable, as evidenced by its high steady-state concentration. A
precise empirical molecular equilibrium structure was derived from a combination of theory and experiment.
MG02
1:47 – 2:02
DETECTION AND STRUCTURAL CHARACTERIZATION OF NITROSAMIDE H2 NNO: A CENTRAL INTERMEDIATE IN deNOx PROCESSES
MICHAEL C McCARTHY, Atomic and Molecular Physics, Harvard-Smithsonian Center for Astrophysics,
Cambridge, MA, USA; KELVIN LEE, School of Chemistry, UNSW, Sydney, NSW, Australia; JOHN F. STANTON, Department of Chemistry, The University of Texas, Austin, TX, USA.
H2 NNO plays a central role as the initial intermediate in the NH2 + NO reaction. As the simplest N -nitrosamine, it is
also the basis for understanding how specific substituents subtly change the structure of the NNO unit in larger nitrosamines,
an important set of compounds that can be produced in foods by nitrites, but which are commonly carcinogenic to humans.
Due to its perceived instability, H2 NNO has never been isolated and spectroscopically characterized in the gas phase, but,
by means of Fourier transform microwave spectroscopy in combination with millimeter-wave double resonance techniques,
the rotational spectrum of the normal and six of its rare isotopic species have been measured to high accuracy between 15
and 90 GHz. For each isotopic species, all three rotational constants have been determined to a fractional accuracy of 10
ppm or better; nitrogen quadrupole coupling constants have also been derived to very high accuracy. By correcting the
experimental rotational constants for vibrational corrections calculated theoretically, a precise semi-experimental structure
has been derived. These findings are consistent with new CCSD(T) calculations which predict that the equilibrium geometry
of H2 NNO is planar, but that it possesses an extremely flat H2 N-X potential, like NH3 . Other aspects of this joint work,
including the bond order inferred from the eQq(N) coupling constants, and the issue of planarity in substituted derivatives of
the form R1 R2 NNO, will be discussed.
48
MG03
MICROWAVE SPECTRA OF 1- AND 2-BROMOBUTANE
2:04 – 2:19
SOOHYUN KA, JIHYUN KIMa , HEESU JANG, JUNG JIN OH, Research Institute of Global Environment,
Sookmyung Women’s University, Seoul, Korea.
Current affiliation: Department of Chemistry, Texas A&M University, College Station, TX 77842-3012, USA
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The rotational spectrum of 1-bromobutane measured by the 480 MHz bandwidth chirped-pulse Fourier transform microwave (CP-FTMW) spectroscopy. In this paper, the ab initio calculation and the analysis of rotational spectrum were
performed, and the properties of gas molecule are reported.
1-bromobutane have five confomers; aa, ag, ga, gg, gg’. The transitions were assigned to three different conformers
which are most stable forms; aa, ag, ga. The spectra for the normal isotopic species and 81 Br substitution were observed and
assigned.
The rotational spectrum of 2-bromobutane has been observed in the frequency region 7-18 GHz. 2-bromobutane has the
three possible conformers; G+, A, G-. The difference of their energy is very small, so the spectra of all conformers were
found in the full range of our spectrum.
Consequentially, the rotational constants, nuclear quadrupole constants, and centrifugal distortion constants were determined and the dipole moment of the aa conformer with 79 Br were measured. All the experimental data is in good agreement
with the calculated data.
MG04
2:21 – 2:36
ACCURATE EQUILIBRIUM STRUCTURES FOR trans-HEXATRIENE BY THE MIXED ESTIMATION METHOD AND
FOR THE THREE ISOMERS OF OCTATETRAENE FROM THEORY; STRUCTURAL CONSEQUENCES OF ELECTRON DELOCALIZATION
NORMAN C. CRAIG, Department of Chemistry and Biochemistry, Oberlin College, Oberlin, OH, USA; JEAN
DEMAISON, Université Lille 1, Laboratoire PhLAM, Villeneuve d’Ascq, France; PETER GRONER, Department of Chemistry, University of Missouri - Kansas City, Kansas City, MO, USA; HEINZ DIETER RUDOLPH,
Department of Chemistry, Universität Ulm, Ulm, Germany; NATALJA VOGT, Section of Chemical Information
Systems, Universität Ulm, Ulm, Germany.
An accurate equilibrium structure of trans-hexatriene has been determined by the mixed estimation method with rotational constants from 8 deuterium and carbon isotopologues and high-level quantum chemical calculations. In the mixed
estimation method bond parameters are fit concurrently to moments of inertia of various isotopologues and to theoretical bond
parameters, each data set carrying appropriate uncertainties. The accuracy of this structure is 0.001 Å and 0.1◦ . Structures of
similar accuracy have been computed for the cis,cis, trans,trans, and cis,trans isomers of octatetraene at the CCSD(T) level
with a basis set of wCVQZ(ae) quality adjusted in accord with the experience gained with trans-hexatriene. The structures
are compared with butadiene and with cis-hexatriene to show how increasing the length of the chain in polyenes leads to
increased blurring of the difference between single and double bonds in the carbon chain. In trans-hexatriene r(“C1 =C2 ”) =
1.339 Å and r(“C3 =C4 ”) = 1.346 Å compared to 1.338 Å for the “double” bond in butadiene; r(“C2 –C3 ”) = 1.449 Å compared
to 1.454 Å for the “single” bond in butadiene. “Double” bonds increase in length; “single” bonds decrease in length.
49
MG05
2:38 – 2:53
RING PUCKERING POTENTIALS OF THREE FLUORINATED CYCLOPENTENES: C5 F8 , C5 HF7 , and C5 H2 F6
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E. A. ARSENAULT, B. E. LONG, WALLACE C. PRINGLE, Department of Chemistry, Wesleyan University,
Middletown, CT, USA; YOON JEONG CHOI, S. A. COOKE, Natural and Social Science, Purchase College
SUNY, Purchase, NY, USA; ESTHER J OCOLA, JAAN LAANE, Department of Chemistry, Texas A & M University, College Station, TX, USA.
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A systematic study on the ring puckering potentials of three fluorinated cyclopentenes
has been performed using Fourier transform microwave spectroscopy in tandem with quantum
chemical calculations. Spectra between 8 GHz
and 16 GHz have been measured for octafluorocyclopentene, 1H-heptafluorocyclopentene, and
1H,2H-hexafluorocyclopentene, where the hydrogens sequentially replace the fluorines on the sp2
hybridized carbons. Rotational constants and centrifugal distortion constants have been determined
for the parent species and all 13 C isotopologues.
In regards to the ring puckering, double minimum
potential, both cross state and intra-state transitions
were observed for all molecules except the 1H,2Hhexafluorocyclopentene. Experimental Coriolis coupling constants and ∆E01 values will be presented and discussed. The
ring puckering barrier heights for C5 F8 , C5 HF7 , and C5 H2 F6 , have been calculated to be 222 cm−1 , 302 cm−1 , and 367
cm−1 , respectively.
MG06
2:55 – 3:10
CONFORMATIONAL TRANSFORMATION OF FIVE-MEMBERED RINGS: THE GAS PHASE STRUCTURE OF 2METHYLTETRAHYDROFURAN
VINH VAN, Institute for Physical Chemistry, RWTH Aachen University, Aachen, Germany; HA VINH LAM
NGUYEN, CNRS et Universités Paris Est et Paris Diderot, Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA), Créteil, France; WOLFGANG STAHL, Institute for Physical Chemistry, RWTH Aachen
University, Aachen, Germany.
2-Methyltetrahydrofuran (2-MeTHF) is a promising environmentally friendly solvent and biofuel component which is
derived from renewable resourcesa . Following the principles of Green Chemistry, 2-MeTHF has been evaluated in various
fields like organometallics, metathesis, and biosynthesis on the way to more eco-friendly synthesesb .
Cyclopentane as the prototype of five-membered rings is well-known to exist as twist or envelope structures. However,
the conformational analysis of its heterocyclic derivative 2-methyl-tetrahydrothiophene (MTTP) yielded two stable twist
conformers and two envelope transition statesc . Here, we report on the heavy atom rs structure of the oxygen-analog of
MTTP, 2-MeTHF, studied by a combination of molecular beam Fourier transform microwave spectroscopy and quantum
chemistry. One conformer of 2-MeTHF was observed and highly accurate molecular parameters were determined using the
XIAM programd . In addition, all 13 C-isotopologues were assigned in natural abundance of 1%. A structural determination
based on the rs positions of all carbon atoms was achieved via Kraitchman’s equationse . The methyl group in 2-MeTHF
undergoes internal rotation and causes A–E splittings of the rotational lines. The barrier was calculated to be 1142 cm−1 at
the MP2/6-311++G(d,p) level of theory, which is rather high. Accordingly, narrow A–E splittings could be observed for only
a few transitions. However, the barrier height could be fitted while the angles between the internal rotor axis and the principal
axes of inertia were taken from the experimental geometry.
a
V. Pace, P. Hoyos, L. Castoldi, P. Domı́nguez de Marı́a, A. R. Alcántara, ChemSusChem 5 (2012), 1369−1379.
a) D. F. Aycock, Org. Process Res. Dev. 11 (2007),156−159. b) M. Smoleń, M. Kȩdziorek, K. Grela, Catal. Commun. 44 (2014), 80−84.
c
V. Van, C. Dindic, H.V.L. Nguyen, W. Stahl, ChemPhysChem 16 (2015), 291−294.
d
H. Hartwig, H. Dreizler, Z. Naturforsch. A 51 (1996), 923−932.
e
J. Kraitchman, Am. J. Phys. 21 (1953), 17−24.
b
50
MG07
3:12 – 3:27
ASSIGNMENT OF THE MICROWAVE SPECTRUM OF 1,2-DIFLUOROBENZENE· · · HCCH: LESSONS LEARNED
FROM ANALYSIS OF A DENSE BROADBAND SPECTRUM
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ANURADHA AKMEEMANA, REBECCA D. NELSON, MIKAYLA L. GRANT, REBECCA A. PEEBLES,
SEAN A. PEEBLES, Department of Chemistry, Eastern Illinois University, Charleston, IL, USA; JUSTIN M.
KANG, Department of Chemistry and Biochemistry, Oberlin College, Oberlin, OH, USA; NATHAN A SEIFERT,
BROOKS PATE, Department of Chemistry, The University of Virginia, Charlottesville, VA, USA.
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Dimers of aromatic molecules with weak proton donors such as acetylene are prototypical systems for investigating
weak CH· · · π interactions. A logical progression from our recent rotational spectroscopic studies of benzene. . . HCCH and
fluorobenzene· · · HCCH was to study 1,2-difluorobenzene(1,2-dfbz)· · · HCCH, so the effect of increasing the number of
electronegative substituents could be investigated. In this talk, structures of benzene, fluorobenzene, and 1,2-difluorobenzene
complexed with HCCH will be compared, and the challenges and pitfalls encountered during assignment of the very rich
chirped-pulse Fourier-transform microwave (CP-FTMW) spectrum will be discussed.
The spectrum of a mixture of 1,2-dfbz and HCCH in a neon carrier was initially recorded using the CP-FTMW spectrometer at the University of Virginia. Transitions matching the patterns and approximate rotational constants predicted for
1,2-dfbz· · · HCCH were readily identified; however, efforts to fit the observed frequencies to an asymmetric top Hamiltonian
were unsuccessful. A second CP-FTMW scan of only 1,2-dfbz monomer revealed that the transitions initially believed to be
1,2-dfbz· · · HCCH were actually present in both scans. Subtraction of lines common to both data sets revealed a previously
unidentified pattern of transitions that have now been confirmed by isotopic substitution to belong to 1,2-dfbz· · · HCCH. The
originally identified transitions are likely 1,2-dfbz· · ·20 Ne, which has a similar mass to the HCCH complex. Ab initio calculations for 1,2-dfbz· · · HCCH and 1,2-dfbz· · · Ne lead to several possible orientations for each dimer with similar energies
and rotational constants, and efforts to improve the computational methods and to reliably identify stationary points on the
dimer potential energy surfaces are ongoing.
MG08
3:29 – 3:39
STRUCTURE DETERMINATION AND CH· · · F INTERACTIONS IN H2 C=CHF· · · H2 C=CF2 BY FOURIERTRANSFORM MICROWAVE SPECTROSCOPY
RACHEL E. DORRIS, REBECCA A. PEEBLES, SEAN A. PEEBLES, Department of Chemistry, Eastern Illinois University, Charleston, IL, USA.
The structure of the weakly bound dimer between fluoroethylene (FE) and 1,1-difluoroethylene (DFE) has been determined using a combination of chirped-pulse and resonant-cavity Fourier-transform microwave spectroscopy over a 7.5 to
19 GHz range. The rotational constants of the most abundant isotopomer were determined to be A = 6601.14(35) MHz, B
= 833.3336(5) MHz and C = 744.0217(5) MHz, and are in excellent agreement with ab initio predictions at the MP2/6311++G(2d,2p) level. Observation of all four unique 13 C isotopologues in natural abundance allowed for a full structure
determination, showing that the dimer takes on a planar configuration with the H–C–F end of FE aligned with one of the
F–C=C–H sides of DFE, forming two inequivalent CH· · · F contacts. The dipole moment components (µa = 0.9002(18) D,
µb = 0.0304(80) D) were determined using Stark effect measurements and confirm the observed structure.
Intermission
51
MG09
3:58 – 4:13
MILLIMETER WAVE SPECTROSCOPY AND EQUILIBRIUM STRUCTURE DETERMINATION OF PYRIMIDINE (mC4 H4 N2 )
ar
y
ZACHARY N. HEIM, BRENT K. AMBERGER, BRIAN J. ESSELMAN, R. CLAUDE WOODS, ROBERT J.
McMAHON, Department of Chemistry, The Univeristy of Wisconsin, Madison, WI, USA.
Pyrimidine, the meta substituted dinitrogen analog of benzene, has been studied in the mm-wave region from 260 – 360
GHz, expanding on previous studies up to 337 GHz.abc The spectra of all four of the singly-substituted 13 C and 15 N isotopologues were observed in natural abundance. Samples of deuterium enriched pyrimidine were synthesized, giving access to
several deuterium-substituted isotopologues. The experimental rotational constants have been corrected for vibration-rotation
coupling and electron mass. The vibration-rotation corrections were calculated with an anharmonic frequency calculation
at the CCSD[T]/ANO1 level using CFOUR. An equilibrium structure determination has been performed using the corrected
rotational constants with the xrefit module of CFOUR. Several vibrational satellites of pyrimidine have also been studied.
Their rotational constants have been compared to those obtained computationally.
c
Z. Kisiel, L. Pszczolkowski, I. R. Medvedev, M. Winnewisser, F. C. De Lucia, E. Herbst, J. Mol. Spectrosc. 233, 231-243 (2005).
G. L. Blackman, R. D. Brown, F. R. Burden, J. Mol. Spectrosc. 35, 444-454 (1970).
W. Caminati, D. Damiani, Chem. Phys. Lett. 179, 460-462 (1991).
in
a
b
MG10
MILLIMETER-WAVE SPECTROSCOPY OF PHENYL ISOCYANATE
4:15 – 4:30
Pr
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CARA E. SCHWARZ, BRENT K. AMBERGER, BENJAMIN C. HAENNI, BRIAN J. ESSELMAN, R.
CLAUDE WOODS, ROBERT J. McMAHON, Department of Chemistry, University of Wisconsin, Madison,
WI, USA.
Phenyl isocyanate (PhNCO) has been studied in the frequency range of 250-360 GHz, improving on rotational and
centrifugal distortion constants based on previous spectroscopic studies between 4.7 and 40 GHz.ab Using the rigid rotor/centrifugal distortion model, many transitions have been assigned for the ground state (approximately 2200 transitions)
and the fundamental of the -NCO torsional vibration (approximately 1500 transitions) for J values ranging between 140 and
210 and Kprolate values from 0 to 42. Beyond these K values, these two spectra show effects of perturbations with other
vibrational states. Vibrational energy levels and vibration-rotation interaction constants were predicted using CFOUR at the
CCSD(T)/ANO0 level. The two lowest energy excited vibrational modes are predicted to have energies of 47 cm−1 (-NCO
torsion) and 95 cm−1 (in-plane -NCO wag). Fermi resonance between the first overtone of the -NCO torsional vibration (94
cm−1 ) and the fundamental of the in-plane -NCO wag has been observed in the spectra of these two states. Analysis for
vibrationally excited states up to 190 cm−1 is in progress.
a
b
A. Bouchy and G. Roussy, Journal of Molecular Spectroscopy. 65 (1977), 395-404.
W. Kasten and H. Dreizler, Z. Naturforsch. 42a (1987), 79-82.
MG11
4:32 – 4:47
BROADBAND MICROWAVE SPECTROSCOPY AS A TOOL TO STUDY THE STRUCTURES OF ODORANT
MOLECULES AND WEAKLY BOUND COMPLEXES IN THE GAS PHASE
SABRINA ZINNa , THOMAS BETZ, CHRIS MEDCRAFT, MELANIE SCHNELL, MPSD, Max Planck Institute for the Structure and Dynamics of Matter, Hamburg, Germany.
The rotational spectrum of trans-cinnamaldehyde ((2E)-3-phenylprop-2-enal) has been obtained with chirped-pulse microwave spectroscopy in the frequency range of 2 - 8.5 GHz. The odorant molecule is the essential component in cinnamon
oil and causes the characteristic smell. In the measured high-resolution spectrum, we were able to assign the rotational spectra
of two conformers of trans-cinnamaldehyde as well as all singly 13 C-substituted species of the lowest-energy conformer in
natural abundance. Two different methods were used to determine the structure from the rotational constants, which will be
compared within this contribution.
In addition, the current progress of studying ether-alcohol complexes, aiming at an improved understanding of the interplay between hydrogen bonding and dispersion interaction, will be reported. Here, a special focus is placed on the complexes
of diphenylether with small aliphatic alcohols.
a
The author thanks ”The Hamburg Centre for Ultrafast Imaging” for financial support.
52
MG12
MICROWAVE SPECTRA OF 9-FLUORENONE AND BENZOPHENONE
4:49 – 5:04
ar
y
CHANNING WEST, GALEN SEDO, Department of Natural Sciences, University of Virginia’s College at Wise,
Wise, VA, USA; JENNIFER VAN WIJNGAARDEN, Department of Chemistry, University of Manitoba, Winnipeg, MB, Canada.
The pure rotational spectra of 9-fluorenone (C13 H8 O) and benzophenone (C13 H10 O) were observed using chirped-pulse
Fourier transform microwave spectroscopy (cp-FTMW). The 9-fluorenone spectrum was collected between 8 and 13 GHz,
which allowed for the assignment of 124 rotational transitions. A separate spectrum spanning from 8 to 14 GHz was collected
for benzophenone, allowing for the assignment of 133 rotational transitions. Both aromatic ketones exhibited strong b-type
spectra with little to no centrifugal distortion, indicating highly rigid molecular structures. A comparison of the experimentally
determined spectral constants of 9-fluorenone to those calculated using both ab initio and density functional theory strongly
suggest the molecule conforms to a planar C2v symmetric geometry as expected for its polycyclic structure. Whereas, a
comparison of the experimental benzophenone constants to those predicted by theory suggests a molecule with non-planar
C2 symmetry, where the two phenyl groups are rotated approximately 32◦ out-of-plane to form a paddlewheel like geometry.
in
MG13
5:06 – 5:21
ASSESSING THE IMPACT OF BACKBONE LENGTH AND CAPPING AGENT ON THE CONFORMATIONAL
PREFERENCES OF A MODEL PEPTIDE: CONFORMATION SPECIFIC IR AND UV SPECTROSCOPY OF 2AMINOISOBUTYRIC ACID
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JOSEPH R. GORD, DANIEL M. HEWETT, Department of Chemistry, Purdue University, West Lafayette, IN,
USA; MATTHEW A. KUBASIK, Department of Chemistry and Biochemistry, Fairfield University, Fairfield, CT,
USA; TIMOTHY S. ZWIER, Department of Chemistry, Purdue University, West Lafayette, IN, USA.
2-Aminoisobutyric acid (Aib) is an achiral, α-amino acid having two equivalent methyl groups attached to Cα . Extended
Aib oligomers are known to have a strong preference for the adoption of a 310 -helical structure in the condensed phase.a Here,
we have taken a simplifying step and focused on the intrinsic folding propensities of Aib by looking at a series of capped
Aib oligomers in the gas phase, free from the influence of solvent molecules and cooled in a supersonic expansion. Resonant
two-photon ionization and IR-UV holeburning have been used to record single-conformation UV spectra using the Z-cap as
the UV chromophore. Resonant ion-dip infrared (RIDIR) spectroscopy provides single-conformation IR spectra in the OH
stretch and NH stretch regions. Data have been collected on a set of Z-(Aib)n -X oligomers with n = 1, 2, 4, 6 and X = -OH and
-OMethyl. The impacts of these capping groups and differences in backbone length have been found to dramatically influence
the conformational space accessed by the molecules studied here. Oligomers of n=4 have sufficient backbone length for a full
turn of the 310 -helix to be formed. Early interpretation of the data collected shows clear spectroscopic markers signaling the
onset of 310 -helix formation as well as evidence of structures incorporating C7 and C14 hydrogen bonded rings.
a
Toniolo, C.; Bonora, G. M.; Barone, V.; Bavoso, A.; Benedetti, E.; Di Blasio, B.; Grimaldi, P.; Lelj, F.; Pavone, V.; Pedone, C., Conformation of Pleionomers of αAminoisobutyric Acid. Macromolecules 1985, 18, 895-902.
MG14
5:23 – 5:38
COMPARISON OF INTRAMOLECULAR FORCES IN DIPEPTIDES WITH TWO AROMATIC RINGS: DOES DISPERSION DOMINATE?
JESSICA A. THOMAS, Department of Biology and Chemistry, Purdue University North Central, Westville, IN,
USA.
IR/UV double resonance spectroscopy has shown that the structure of the capped dipeptide Ac-Trp-Tyr-NH2 is dominated
by a hydrophobic interaction between the aromatic rings on the side chains. Using the same method, a similar molecule, AcPhe-Phe-NH2 , had three experimentally observed conformers including one similar to that of Ac-Trp-Tyr-NH2 . In this work,
calculations were performed on additional dipeptides containing two aromatic rings to determine if the dispersion-dominated
structure was among the lowest energy structures in all such cases.
The B3LYP-DCP method developed by DiLabio and Torres was used to calculate the conformations of each dipeptide.
Appending dispersion correction potentials (DCP) to B3LYP input files improves results for systems containing dispersion
interactions without significantly increasing the calculation time. This method was used first on Ac-Trp-Tyr-NH2 and Ac-PhePhe-NH2 to confirm that it successfully identified the experimentally observed structures among the lowest energy results and
was then applied to other capped dipeptides containing two aromatic rings including Ac-Phe-Tyr-NH2 and Ac-Tyr-Phe-NH2 .
53
MH. Linelists
Monday, June 22, 2015 – 1:30 PM
Chair: Shanshan Yu, California Institute of Technology, Pasadena, CA, USA
MH01
1:30 – 1:45
st
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HITRAN IN THE XXI CENTURY: BEYOND VOIGT AND BEYOND EARTH
LAURENCE S. ROTHMAN, IOULI E GORDON, CHRISTIAN HILL, ROMAN V KOCHANOV, PIOTR
WCISLO, Atomic and Molecular Physics, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA;
JONAS WILZEWSKI, Department of Astronomy, Harvard University, Cambridge, MA, USA.
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The line-by-line portion of the most recent HITRAN2012 editiona contains spectroscopic parameters for 47 gases and
associated isotopologues. Continuing the effort of the last five decades, our task has been to improve the accuracy of the
existing parameters as well as to add new bands, molecules, and their isotopologues. In this talk we will briefly summarize
some of the most important efforts of the past year.
Particular attention will be given to explaining the new development in providing line-shape information in HITRAN.
There are two important directions in which the database is evolving with respect to line shapes. The first direction is that,
apart from the Voigt profile parameters that were traditionally provided in HITRAN, we are able to add parameters associated
with many “mainstream” line shapes, including Galatry, speed-dependent Voigt, and the HT profileb recently recommended
by IUPACc . As a test case, we created a first complete dataset of the HT parameters for every line of molecular hydrogen in
the HITRAN database. Another important development is that in order to increase the potential of the HITRAN database in
planetary sciences, experimental and theoretical line-broadening coefficients, line shifts and temperature-dependence exponents of molecules of planetary interest broadened by H2 , He, and CO2 have been assembled from available peer-reviewed
sources. The collected data were used to create semi-empirical models for calculating relevant parameters for every line of
the studied molecules in HITRAN.
This work has been supported by NASA Aura Science Team Grant NNX14AI55G and NASA Planetary Atmospheres Grant NNX13AI59G.
a
L.S. Rothman, et al. “The HITRAN 2012 molecular spectroscopic database,” JQSRT 130, 4–50 (2013).
N.H. Ngo, et al. “An isolated line-shape model to go beyond the Voigt profile in spectroscopic databases and radiative transfer codes,” JQSRT 129, 89–100 (2013).
c
J. Tennyson, et al. “Recommended isolated-line profile for representing high-resolution spectroscopic transitions,” Pure Appl.Chem. 86, 1931–1943 (2014).
b
MH02
1:47 – 2:02
HITRANonline: A NEW STRUCTURE AND INTERFACE FOR HITRAN LINE LISTS AND CROSS SECTIONS
CHRISTIAN HILL, LAURENCE S. ROTHMAN, IOULI E GORDON, ROMAN V KOCHANOV, PIOTR
WCISLO, Atomic and Molecular Physics, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA;
We present HITRANonline, an online interface to the internationally-recognised HITRAN molecular spectroscopic
database[1], and describe the structure of its relational database backend[2].
As the amount and complexity of spectroscopic data on molecules used in atmospheric modelling has increased, the
existing 160-character, text-based format has become inadequate for its description. For example, line shapes such as the
Hartmann-Tran profile[3] require up to six parameters for their full description (each with uncertainties and references), data
is available on line-broadening by species other than “air” and “self” and more than the current maximum of 10 isotopologues of some molecules (for example, CO2 ) can be important for accurate radiative-transfer modelling. The new relational
database structure overcomes all of these limitations as well as allowing for better data provenance through “timestamping”
of transitions and a direct link between items of data and their literature sources.
To take full advantage of this new database structure, the online interface HITRANonline, available at www.hitran.org,
provides a user-friendly way to make queries of HITRAN data with the option of returning it in a customizable format with
user-defined fields and precisions. Binary formats such as HDF-5 are also supported. In addition to the data, each query also
produces its own bibliography (in HTML and BibTeX formats), “README” documentation and interactive graph for easy
visualization.
1. L. S. Rothman et al., JSQRT 130, 4-50 (2013).
2. C. Hill, I. E. Gordon, L. S. Rothman, J. Tennyson, JQSRT130, 51-61 (2013).
3. N. H. Ngo, D. Lisak, H. Tran, J.-M. Hartmann, JQSRT 129, 89–100, (2013); erratum: JQSRT 134, 105 (2014).
This work has been supported by NASA Aura Science Team Grant NNX14AI55G and NASA Planetary Atmospheres
Grant NNX13AI59G.
54
MH03
2:04 – 2:19
WORKING WITH HITRAN DATABASE USING HAPI: HITRAN APPLICATION PROGRAMMING INTERFACE
ar
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ROMAN V KOCHANOVa , CHRISTIAN HILL, PIOTR WCISLO, IOULI E GORDON, LAURENCE S. ROTHMAN, Atomic and Molecular Physics, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA;
in
A HITRAN Application Programing Interface (HAPI) has been developed to allow users on their local machines much
more flexibility and power. HAPI is a programming interface for the main data-searching capabilities of the new “HITRANonline” web service (http://www.hitran.org). It provides the possibility to query spectroscopic data from the HITRANb
database in a flexible manner using either functions or query language. Some of the prominent current features of HAPI
are: a) Downloading line-by-line data from the HITRANonline site to a local machine b) Filtering and processing the data in
SQL-like fashion c) Conventional Python structures (lists, tuples, and dictionaries) for representing spectroscopic data d) Possibility to use a large set of third-party Python libraries to work with the data e) Python implementation of the HT lineshapec
which can be reduced to a number of conventional line profiles f) Python implementation of total internal partition sums
(TIPS-2011d ) for spectra simulations g) High-resolution spectra calculation accounting for pressure, temperature and optical
path length h) Providing instrumental functions to simulate experimental spectra i) Possibility to extend HAPI’s functionality
by custom line profiles, partitions sums and instrumental functions
Currently the API is a module written in Python and uses Numpy library providing fast array operations. The API is
designed to deal with data in multiple formats such as ASCII, CSV, HDF5 and XSAMS.
This work has been supported by NASA Aura Science Team Grant NNX14AI55G and NASA Planetary Atmospheres
Grant NNX13AI59G.
a
QUAMER, Tomsk State University, Tomsk, Russia
L.S. Rothman et al. JQSRT, Volume 130, 2013, Pages 4-50
c
N.H. Ngo et al. JQSRT, Volume 129, November 2013, Pages 89–100
d
A. L. Laraia at al. Icarus, Volume 215, Issue 1, September 2011, Pages 391–400
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b
MH04
2:21 – 2:31
GPU ACCELERATED INTENSITIES: A NEW METHOD OF COMPUTING EINSTEIN-A COEFFICIENTS
AHMED FARIS AL-REFAIE, Department of Physics and Astronomy, University College London, Gower Street,
London WC1E 6BT, United Kingdom; SERGEI N. YURCHENKO, Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT, United Kingdom; JONATHAN TENNYSON, Department of Physics and Astronomy, University College London, London, IX, United Kingdom.
Abstract
The use of variational nuclear motion calculations to produce comprehensive molecular line lists is now becoming common. In order to produce high quality and complete line-lists in particular applicable to high temperatures requires large
amounts of computational resources. The more accuracy required, the larger the problem and the more computational resources needed. The two main bottlenecks in the production of these line-lists are solving the eigenvalue problem and the
computation of the Einstein-A coefficients. From the project’s recently released line-lists, the number of transitions can reach
up to 10 billion evaluated by the combination of millions of eigenvalues and eigenvectors corresponding to individual energy
states. For line-lists of this size, the evaluation of Einstein-A coefficients take up the vast majority of computational time
compared to solving the eigenvalue problem. Recently, as part of the ExoMol [1] project, we have developed a new program
called GPU Accelerated INtensities (GAIN) that utilises the highly parallel Graphics Processing Units (GPU) in order to
accelerate the evaluation of the Einstein-A coefficients. Speed-ups of up to 70x can be achieved on a single GPU and can be
further improved by utilising multiple GPUs. The GPU hardware, its limitations and how the problem was implemented to
exploit parallelism will be discussed.
References
[1] J. Tennyson and S. N. Yurchenko. ExoMol: molecular line lists for exoplanet and other atmospheres. MNRAS, 425:21–33,
2012.
55
MH05
2:33 – 2:48
LINE SHAPE PARAMETERS FOR NEAR INFRARED CO2 BANDS IN THE 1.61 AND 2.06 MICRON SPECTRAL
REGIONS
ar
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V. MALATHY DEVI, D. CHRIS BENNER, Department of Physics, College of William and Mary, Williamsburg,
VA, USA; KEEYOON SUNG, LINDA BROWN, TIMOTHY J CRAWFORD, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, USA; MARY ANN H. SMITH, Science Directorate, NASA Langley
Research Center, Hampton, VA, USA; ARLAN MANTZ, Department of Physics, Astronomy and Geophysics,
Connecticut College, New London, CT, USA.
a
in
Accurate spectroscopic measurements of self- and air-broadened Lorentz half-width and pressure-shift coefficients and
their temperature dependence exponents are crucial for the Orbiting Carbon Observatory (OCO-2) mission.a We therefore
analyzed 73 high-resolution high signal-to-noise spectra of CO2 and CO2 +air for OCO-2 channels at 1.61 and 2.06 µm.
These spectra were recorded at various spectral resolutions (0.004-0.013 cm−1 ) using two spectrometers (the Kitt Peak FTS
in Arizona and the Bruker 125HR FTS at the Jet Propulsion Laboratory in Pasadena, California). Six different absorption
cells with path lengths between 0.2 and 121 m were used with gas samples at a range of temperatures (170-297 K). The gas
pressures ranged from (0.3-898 Torr for pure sample and 26-924 Torr for mixtures of CO2 and air with CO2 volume mixing
ratios between 0.01 and 0.4. The cold sample spectra were acquired using a short 0.2038 m straight pass celland a multipass
Herriott cell having a 20.941 m total path A multispectrum fitting technique was employed to fit all the spectra simultaneously
with a non-Voigt line shape profile including speed dependence and full line mixing. Examples of fitted spectra and retrieved
parameters in both CO2 band regions will be shown. Comparisons of some of the results with other published values will be
provided.b
D. Crisp, B.M. Fisher, C. O’Dell, et.al., Atmos. Meas. Tech. Discuss 4 (2011) 1-59.
Research described in this paper are performed at the College of William and Mary, Jet Propulsion Laboratory, California Institute of Technology, NASA Langley Research
Center and Connecticut College under contracts and cooperative agreements with the National Aeronautics and Space Administration.
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MH06
2:50 – 3:05
RELIABLE IR LINE LISTS FOR SO2 AND CO2 ISOTOPOLOGUES COMPUTED FOR ATMOSPHERIC MODELING
ON VENUS AND EXOPLANETS
XINCHUAN HUANG, Carl Sagan Center, SETI Institute, Moutain View, CA, USA; DAVID SCHWENKE, MS
258-2, NAS Facility, NASA Ames Research Center, Moffett Field, CA, USA; TIMOTHY LEE, Space Science
and Astrobiology Division, NASA Ames Research Center, Moffett Field, CA, USA; ROBERT R. GAMACHE,
Department of Environmental, Earth, and Atmospheric Sciences, University of Massachusetts, Lowell, MA, USA.
For SO2 atmospheric characterization in Venus and other Exoplanetary environments, recently we presented Ames296K line lists for 626 (upgraded) and other 4 symmetric isotopologues: 636, 646, 666 and 828. For CO2 , we reported
Ames-296K (1E-42 cm/molecule) and Ames-1000K (1E-36 cm/molecule) IR line lists up to E’=18000 cm−1 for 13 CO2
isotopologues, including symmetric species 626, 636, 646, 727, 737, 828, 838, and asymmetric species 627, 628, 637, 638,
728, 738. CO2 line shape parameters were also determined for four different temperature ranges: Mars, Earth, Venus, and
higher temperatures. General line position prediction accuracy up to 5000 cm−1 (SO2 ) or 13000 cm−1 (CO2 ) is 0.01 – 0.02
cm−1 . Most transition intensity deviations are less than 5-10%, when compare to experimentally measured quantities. With
such prediction accuracy, these SO2 and CO2 isotopologue lists are the best available alternative for those wide spectra region
missing from spectroscopic databases such as HITRAN and CDMS. For example, only very limited data exist for SO2 646/636
and no data at all for other minor isotopologues. They should greatly facilitate spectroscopic analyses in future laboratory or
astronomical observations. Our line list work are based on ”Best Theory + Reliable High-Resolution Experiment” strategy,
i.e. using an ab initio potential energy surface refined with selected reliable high resolution experimental data, and high quality
CCSD(T)/aug-cc-pVQ(or Q+d)Z dipole moment surfaces. Note that we have solved a convergence defect on SO2 Ames-1
PES and further improved the quality and completeness of the Ames-296K SO2 list by including most recent experimental
data into the refinement. We will compare the Ames-296K SO2 and CO2 lists to latest experiments and HITRAN/CDMS
models. We expect more interactions between experimental and theoretical efforts. Currently the Ames-296K lists are
available at http://huang.seti.org/.
56
MH07
3:07 – 3:22
2
+
2
+
LASER SPECTROSCOPIC STUDY OF CaH IN THE B Σ AND D Σ STATES
KYOHEI WATANABE, KANAKO UCHIDA, KAORI KOBAYASHI, FUSAKAZU MATSUSHIMA, YOSHIKI
MORIWAKI, Department of Physics, University of Toyama, Toyama, Japan.
in
ar
y
Calcium hydride is one of the abundant molecules in the stellar environment, and is considered as a probe of stellar
analysisa . Ab initio calculations have shown that the electronic excited states of CaH have complex potential curves. It is suggested that the B2 Σ+ state has an interesting double minimum potential due to the avoided crossingb . Such a potential leads
to drastic change of the rotational constants when the vibrational energy level goes across the potential barrier. Spectroscopic
studies on CaH began in the 1920’sc , and many studies have been carried out since then. Bell et al. extensively assigned the
D2 Σ+ −X2 Σ+ bands in the UV regiond . Bernath’s group has observed transitions in the IR and visible regions and identified
their upper states as the A2 Σ+ , B2 Σ+ and E2 Σ+ statesefgh . We have carried out a laser induced fluorescence (LIF) study in
the UV region between 360 and 430 nm. We have produced CaH by using laser ablation of a calcium target in a hydrogen gas
environment, then molecules have been excited by a second harmonic pulse of dye laser and the fluorescence from molecules
have been detected through a monochromator. Detection of the D2 Σ+ -X2 Σ+ bands already identified by Bell et al. indicates
the production of CaH. In addition, many other bands have been also found and a few bands have been assigned by using the
combination differences, the lower state of these bands have been confirmed to the vibrational ground state of X2 Σ+ state.
We have tentatively assigned these bands as the B2 Σ+ −X2 Σ+ transition. We will discuss the assignment of these bands,
together with the rotational constants comparing with those calculated from the ab initio potential.
a
B. Barbuy, R. P. Schiavon, J. Gregorio-Hetem, P. D. Singh C. Batalha , Astron. Astrophys. Sippl. Ser. 101, 409 (1993).
P. F. Weck and P. C .Stabcil, J. Chem. Phys. 118, 9997 (2003).
c
R. S. Mulliken, Phys. Rev. 25, 509 (1925).
d
G. D. Bell, M, Herman, J. W. C. Johns, and E. R. Peck, Physica Scripta 20, 609 (1979).
e
A. Shayesteh, K. A. Walker, I. Gordon, D. R. T. Appadoo, and P. F. Bernath, J. Mol. Struct. 695-696, 23 (2004).
f
R. S. Ram, K. Tereszchuk, I. E. Gordon, K. A. Walker, and P. F. Bernath, J. Mol. Spec. 266, 86 (2011).
g
G. Li, J. J. Harrison, R. S. Ram, C. M. Western, and P. F. Bernath Quant. Spectrosc. Rad. Transfer. 113, 67 (2012).
h
A. Shayesteh, R. S. Ram, and P. F. Bernath, J. Mol. Spec. 288, 46 (2013).
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Intermission
MH08
ADDITIONAL MEASUREMENTS AND ANALYSES OF
H17
2 O
AND
3:41 – 3:56
H18
2 O
JOHN PEARSON, SHANSHAN YU, Jet Propulsion Laboratory, California Institute of Technology, Pasadena,
CA, USA; ADAM WALTERS, IRAP, Université de Toulouse 3 - CNRS - OMP, Toulouse, France.
Historically the analysis of the spectrum of water has been a balance between the quality of the data set and the applicability of the Hamiltonian to a highly non-rigid molecule. Recently, a number of different non-rigid analysis approaches have
successfully been applied to 16 O water resulting in a self-consistent set of transitions and energy levels to high J which allowed
the spectrum to be modeled to experimental precisionab . The data set for 17 O and 18 O water was previously reviewed and
many of the problematic measurements identifiedc , but Hamiltonian modeling of the remaining data resulted in significantly
poorer quality fits than that for the 16 O parent. As a result, we have made additional microwave measurements and modeled
the existing 17 O and 18 O data sets with an Euler series modeld . This effort has illuminated a number of additional problematic
measurements in the previous data sets and has resulted in analyses of 17 O and 18 O water that are of similar quality to the
16
O analysis. We report the new lines, the analyses and make recommendations on the quality of the experimental data sets.
a
SS. Yu, J.C. Pearson, B.J. Drouin et al. J. Mol. Spectrosc. 279, 16-25 (2012)
J. Tennyson, P.F. Bernath, L.R. Brown et al. J. Quant. Spectrosc. Rad. Trans. 117, 29-58 (2013)
J. Tennyson, P.F. Bernath, L.R. Brown et al. J. Quant. Spectrosc. Rad. Trans. 110, 573-596 (2009)
d
H.M. Pickett, J.C. Pearson, C.E. Miller J. Mol. Spectrosc. 233, 174-179 (2005)
b
c
57
MH09
EXPERIMENTAL LINE LISTS OF HOT METHANE
3:58 – 4:13
ar
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ROBERT J. HARGREAVES, PETER F. BERNATH, Department of Chemistry and Biochemistry, Old Dominion
University, Norfolk, VA, USA; JEREMY BAILEY, School of Physics, University of New South Wales, New South
Wales, Australia; MICHAEL DULICK, Department of Chemistry and Biochemistry, Old Dominion University,
Norfolk, VA, USA.
in
Line lists of CH4 at high temperatures (up to 900◦ C) have been produced between 2500 and 5000 cm−1 . This spectral
range contains the pentad and octad regions, and includes numerous fundamental, overtone and hot bands. Our method makes
use of a quartz sample cell that is heated by a tube furnace. Four spectra are then recorded at each temperature using a Fourier
transform infrared spectrometer at high resolution (0.02 cm−1 ). By combining these four spectra at each temperature, the
emission and absorption from the cell and molecules are accounted for, and we obtain the true transmission spectrum of hot
CH4 . Analysis of this series of spectra enables the production of line lists that include positions, intensities and empirical
lower state energies.
We also compare our line lists to the best available theoretical line lists at high temperatures. Whilst our experimental line
lists contain fewer lines than theoretical line lists, we are able to demonstrate the quality of our observed spectra by considering
our observations as absorption cross sections. This is important at elevated temperatures, when numerous blended lines appear
as a continuum.
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MH10
EXPERIMENTAL TRANSMISSION SPECTRA OF HOT AMMONIA IN THE INFRARED
4:15 – 4:30
CHRISTOPHER A. BEALE, Department of Ocean, Earth and Atmospheric Sciences, Old Dominion University,
Norfolk, VA, USA; ROBERT J. HARGREAVES, MICHAEL DULICK, PETER F. BERNATH, Department of
Chemistry and Biochemistry, Old Dominion University, Norfolk, VA, USA.
High resolution absorption spectra of hot ammonia have been recorded in the 2400–5500 cm−1 region and the line lists
are presented. This extends our previous work on ammonia in the 740–4000 cm−1 regiona,b and utilizes our improved cell
design that has been successfully applied to methane in a similar spectral region. Transmission spectra were acquired for
seven temperatures up to 700◦ C using a Bruker IFS 125HR Fourier transform spectrometer and empirical lower state energies
are obtained from the temperature dependence of intensities. Applications of our spectra and line lists include modeling of
brown dwarfs and (exo)planetary atmospheres.
a
b
R.J. Hargreaves, G. Li and P.F. Bernath. 2011, ApJ, 735, 111
R.J. Hargreaves, G. Li and P.F. Bernath. 2011, JQSRT, 113, 670
MH11
HYPERSONIC POST-SHOCK CAVITY RING-DOWN SPECTROSCOPY
4:32 – 4:47
NICOLAS SUAS-DAVID, IPR UMR6251, CNRS - Université Rennes 1, Rennes, France; SAMIR KASSI,
UMR5588 LIPhy, Université Grenoble 1/CNRS, Saint Martin D’heres, France; ABDESSAMAD BENIDAR,
ROBERT GEORGES, IPR UMR6251, CNRS - Université Rennes 1, Rennes, France.
A highly sensitive experimental set-up (αmin = 10−10 cm−1 ) has been developed to produce high-temperature infrared
spectra of methane in the Tetradecad polyad region (1.67 µm) using cw-CRDS. A continuous flow of methane admixed
to argon is initially heated at 1000 – 1500 K and then accelerated to hypersonic speeds in a vacuum chamber before being
abruptly stopped by the impact on a planar screen set perpendicular to the flow axis, forming a stationary shock wave detached
from the screen (bow shock). The CRD optical beam probes the very hot subsonic zone behind the shock where the gas
temperature is close to the stagnation one. Computational Fluid Dynamics calculations have been performed to characterize
the post-shock structure of the flow. Spectra reveal a series of new hot bands of fundamental interest for the modeling of
highly excited levels of methane.
58
MH12
4:49 – 5:04
CH3 D NEAR INFRARED CAVITY RING-DOWN SPECTRUM REANALYSIS AND IR-IR DOUBLE RESONANCE
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SHAOYUE YANG, GEORGE SCHWARTZ, Department of Physics, The University of Virginia, Charlottesville,
VA, USA; KEVIN LEHMANN, Departments of Chemistry and Physics, University of Virginia, Charlottesville,
VA, USA.
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As one of the most important hydrocarbon prototype molecules, CH3 D’s overtone band in near infrared region has not
been well studied. Various methods were used to help identifying transitions from previous cavity ring down spectrum of
CH3 D in the near infrared region. Symmetric top molecules’ Hamiltonian diagonal terms for the ground state, perpendicular
state and parallel state were simulated by software PGopher. Combination differences were used to find possible pairs of
transitions starting from adjacent ground state and ending in same excited states. Also we introduced our temperature controlled spectrum setup for ground state energy and rotational quanta prediction from temperature dependence, and proven to
be working well for lower J levels for CH4 . At last, we set up a double resonance system, using two lasers (3.3 and 1.65 µm,
respectively) to excite transitions from the same ground state, to provide strong proof for the lower state quanta.
MH13
AYTY: A NEW LINE-LIST FOR HOT FORMALDEHYDE
5:06 – 5:21
AHMED FARIS AL-REFAIE, Department of Physics and Astronomy, University College London, Gower Street,
London WC1E 6BT, United Kingdom; SERGEI N. YURCHENKO, Department of Physics and Astronomy,
University College London, Gower Street, London WC1E 6BT, United Kingdom; JONATHAN TENNYSON,
Department of Physics and Astronomy, University College London, London, IX, United Kingdom; ANDREY
YACHMENEV, Department of Physics and Astronomy, University College London, Gower Street, London WC1E
6BT, United Kingdom.
Abstract
The ExoMol [1] project aims at providing spectroscopic data for key molecules that can be used to characterize the atmospheres of exoplanets and cool stars. Formaldehyde (H2 CO) is of growing importance in studying and modelling terrestrial
atmospheric chemistry and dynamics. It also has relevance in astrophysical phenomena that include interstellar medium
abundance, proto-planetary and cometary ice chemistry and masers from extra-galactic sources. However there gaps in currently available absolute intensities and a lack of higher rotational excitations that makes it unfeasible to accurately model
high temperature systems such as hot Jupiters. Here we present AYTY [2], a new line list for formaldehyde applicable to
temperatures up to 1500 K. AYTY contains almost 10 million states reaching rotational excitations up to J = 70 and over
10 billion transitions at up to 10 000 cm−1 . The line list was computed using the variational ro-vibrational solver TROVE
with a refined ab-initio potential energy surface and dipole moment surface.
References
[1] J. Tennyson and S. N. Yurchenko. MNRAS, 425:21–33, 2012.
[2] A. F. Al-Refaie, S. N. Yurchenko, A. Yachmenev, and J. Tennyson. MNRAS, 2015.
59
MH14
5:23 – 5:38
THE MICROWAVE SPECTROSCOPY OF AMINOACETONITRILE IN THE VIBRATIONAL EXCITED STATE
CHIHO FUJITA, HIROYUKI OZEKI, Department of Environmental Science, Toho University, Funabashi,
Japan; KAORI KOBAYASHI, Department of Physics, University of Toyama, Toyama, Japan.
A. Belloche, K. M. Menten, C. Comito, H. S. P. Müller, P. Schilke, J. Ott, S. Thorwirth, and C. Hieret, 2008, Astronom. & Astrophys. 482, 179 (2008).
Y. Motoki, Y. Tsunoda, H. Ozeki, and K. Kobayashi, Astrophys. J. Suppl. Ser. 209, 23 (2013).
B. Bak, E. L. Hansen, F. M. Nicolaisen, and O. F. Nielsen, Can. J. Phys. 53, 2183 (1975).
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a
b
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Aminoacetonitrile (NH2 CH2 CN) is a potential precursor of the simplest amino acid, glycine and was detected toward
SgrB2(N). a It is expected that the strongest transitions will be found in the terahertz region so that we have extended measurements up to 1.3 THz. b This study gave an accurate prediction of aminoacetonitrile up to 2 THz which is useful for
astronomically search. This molecule has a few low-lying vibrational excited states and the pure rotational transitions in these
vibrational excited states are expected to found. c We found a series of transitions with intensity of about 30%. Eighty-eight
spectral lines including both a-type and b-type transitions were recorded in the frequency region of 400 - 450 GHz, and centrifugal distortion constants up to the sextic term were determined. Perturbation was recognized. We will report the current
status of the analysis.
60
MI. Ions
Monday, June 22, 2015 – 1:30 PM
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Chair: Mark Johnson, Yale University, New Haven, CT, USA
MI01
ROTATIONAL ACTION SPECTROSCOPY VIA STATE-SELECTIVE HELIUM ATTACHMENT
LARS KLUGE, ALEXANDER STOFFELSa , SANDRA BRÜNKEN, OSKAR
STEPHAN SCHLEMMER, I. Physikalisches Institut, Universität zu Köln, Köln, Germany.
1:30 – 1:45
ASVANY,
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Helium atoms can attach to molecular cations via ternary collision processes forming weakly bound (≈ 1 kcal/mol)
He-M+ complexes. We developed a novel sensitive action spectroscopic scheme for molecular ions based on an observed
rotational state dependency of the He attachment process [1]. A detailed account of the underlying kinetics will be presented
on the example of the CD+ ion, where our studies indicate a decrease of around 50% for the rotational state dependent
ternary He attachment rate coefficient of the J = 1 level with respect to the J = 0 level. Experiments are performed on
mass-selected ions stored in a temperature-variable (T ≥ 3.9 K) cryogenic rf 22-pole ion trap in the presence of a high
number density of He (≈ 1015 cm−3 ) [2]. Rotational spectra of the bare ions are recorded by measuring the change in the
number of formed He-M+ complexes after a certain storage time as a function of excitation wavelength. Here we will also
present the first measurements of the rotational ground state transitions of CF+ (J = 1 − 0, hfs resolved) and NH3 D+
(JK = 10 − 00 ), recorded in this way.
[1] Brünken et al., ApJL 783, L4 (2014)
[2] Asvany et al., Applied Physics B 114, 203 (2014)
a
also at: Institute for Molecules and Materials (IMM), Radboud University Nijmegen, Nijmegen, Netherlands
MI02
1:47 – 2:02
SYMMETRY BEYOND PERTURBATION THEORY: FLOPPY MOLECULES AND ROTATION-VIBRATION STATES
HANNO SCHMIEDT, STEPHAN SCHLEMMER, I. Physikalisches Institut, University of Cologne, Cologne,
Germany; PER JENSEN, Fachbereich C-Physikalische und Theoretische Chemie, Bergische Universität Wuppertal, D-42097 Wuppertal, Germany.
In the customary approach to the theoretical description of the nuclear motion in molecules, the molecule is seen as a nearstatic structure rotating in space. Vibrational motion causing small structural deformations induces a perturbative treatment
of the rotation-vibration interaction, which fails in fluxional molecules, where all vibrational motions are large compared to
a
the linear extension of the molecule. An example is protonated methane (CH+
5 ) . For this molecule, customary theory fails
to simulate reliably even the low-energy spectrum. Within the traditional view of rotation and vibration being near-separable,
rotational and vibrational wavefunctions can be symmetry classified separately in the molecular symmetry (MS) group b . In
the present contribution we discuss a fundamental group theoretical approach to the problem of determining the symmetries of
molecular rotation-vibration states. We will show that all MS groups discussed so far are subgroups of the special orthogonal
group in three dimensions SO(3)c . This leads to a group theoretical foundation of the technique of equivalent rotations d . The
MS group of protonated methane (G240 ) represents, to the best of our knowledge, the first example of an MS group which is
not a subgroup of SO(3) (nor of O(3) nor of SU(2)). Because of this, a separate symmetry classification of vibrational and
rotational wavefunctions becomes impossible in this MS group, consistent with the fact that a decoupling of vibrational and
rotational motion is impossible. We want to discuss the consequences of this. In conclusion, we show that the prototypical
floppy molecule CH+
5 represents a new class of molecules, where usual group theoretical methods for determining selection
rules and spectral assignments fail so that new methods have to be developed.
a
P. Kumar and D. Marx, Physical Chemistry Chemical Physics 8, 573 (2006); Z. Jin, B. J. Braams, and J. M. Bowman, The Journal of Physical Chemistry A 110, 1569 (2006);
A. S. Petit, J. E. Ford, and A. B. McCoy, The Journal of Physical Chemistry A 118, 7206 (2014).
b
P.R. Bunker and P. Jensen, Molecular Symmetry and Spectroscopy (NRC Research Press, Ottawa, Canada, 1998).
c
Being precise, we must include O(3) and SU(2), but our theory can be easily extended to these two groups.
d
H. Longuet-Higgins, Molecular Physics 6, 445 (1963).
61
MI03
2:04 – 2:19
STUDYING ROTATION/TORSION COUPLING IN
H+
5
USING DIFFUSION MONTE CARLO
MELANIE L. MARLETT, ZHOU LIN, ANNE B McCOY, Department of Chemistry and Biochemistry, The
Ohio State University, Columbus, OH, USA.
in
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H+
5 is a highly fluxional intermediate found in interstellar clouds. The rotational/torsional couplings in this molecule are
of great interest due to the unusually large coupling between these modes. However, theoretical studies of highly fluxional
molecules like H+
5 are challenging due to the lack of a good zero-order model. In order to better understand the rotation/vibration interaction, a method has been developed to model the rotational/torsional motions. This method is based upon
diffusion Monte Carlo (DMC). In this approach, the vibrational contribution to the wavefunction is modeled using standard
DMC approaches, while the rotational/torsional contribution is treated as a set of coefficients that are assigned to the various
rotational/torsional state vectors. The potential portion of the Hamiltonian is expressed as a low-order expansion in terms of
the torsion angle between the two outer H2 units. The expansion coefficients are evaluated at each time step for each walker
and depend on the 3N − 7 other internal coordinates. The transition frequencies obtained from this method for J ≤ 1 agree
well with results obtained using other methods such as fixed-node diffusion Monte Carlo.a This new method is advantageous
over the fixed-node approach because it allows for multiple state calculations at once which saves on computation time.
a
Sarka, J.; Fábri, C.; Szidarovszky, T.; Császár, A.G.; Lin Z.; McCoy, A.B., “Modeling Rotations, Vibrations, and Rovibrational Couplings in Astructural Molecules - A Case
Study Based on the H+
5 Molecular Ion.”, accepted by Mol. Phys.
MI04
2:21 – 2:36
+
C ISOTOPOLOGUES OF HCO MEASURED BY USING EVENSON-TYPE TUN-
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HIGH-J ROTATIONAL LINES OF
ABLE FIR SPECTROMETER
13
MARI SUZUKI, RYO OISHI, YOSHIKI MORIWAKI, FUSAKAZU MATSUSHIMA, Department of Physics,
University of Toyama, Toyama, Japan; TAKAYOSHI AMANO, Jet Propulsion Laboratory, California Institute
of Technology, Pasadena, CA, USA.
Frequencies of high-J rotational lines of HCO+ and its isotopologues have been measured precisely by using an Evensontype spectrometer in Toyama. The tunable far-infrared spectrometer (TuFIR in short) is based on synthesizing terahertz
radiation from two mid-infrared CO2 laser lines and one microwave source. Study of the isotopologues containing H or D,
12
C, and 16 O were reported last year. In the present work, isotopologues of H or D, 13 C, and 16 O have been studied. The
HCO+ ions are produced by discharging a 13 CO, H2 (or D2 ), and Ar mixture in an extended negative glow discharge cell
cooled with liquid nitrogen. Because the low-J rotational lines have been investigated by other groups, our present study
was focussed mainly to the measurements of higher-J rotational lines. Currently we have observed the lines J + 1 ← J(J=11,
13-21) for H13 CO+ , and J + 1 ← J (J=13-18, 20-22, 24-25) for D13 CO+ . Molecular contstants for these isotopologues (B, D,
H, L) have been modified. From the analysis of the intensity of each rotational line, we estimate the rotational temperature to
be as low as 140K. This low temperature makes it difficult to measure yet higher-J lines. Measurement of other isotopogues
such as those containing oxygen isotopes is now in preparation.
MI05
2:38 – 2:48
UV-UV HOLE-BURNING SPECTROSCOPY OF A PROTONATED ADENINE DIMER IN A COLD QUADRUPOLE ION
TRAP
HYUK KANG, Department of Chemistry, Ajou University, Suwon, Korea.
A novel method for double-resonance photofragmentation spectroscopy in a cold quadrupole ion trap has been developed
and utilized to differentiate the structures of a cold protonated adenine dimer. A burn laser generates a population hole of a
certain conformer of the dimer stored in a cold quadrupole ion trap, and an auxiliary dipolar RF ejects the photofragments
by the burn laser from the trap. A probe laser detects depletion of a certain conformer by the burn laser, and a conformerspecific UV or IR spectrum of a cold ion is obtained by scanning the wavelength of the burn or the probe laser. This simple and
versatile method is applicable to any type of double-resonance photofragmentation spectroscopy in a cold quadrupole ion trap.
To demonstrate its capability, it was applied to UV-UV hole-burning spectroscopy of a protonated adenine dimer. It is proved
that a cold protonated adenine dimer has at least two hydrogen-bonding geometries and each has multiple electronically
excited states with significantly different spectral bandwidths, possibly due to different excited state dynamics.
62
MI06
2:50 – 3:05
SPECTROSCOPIC INVESTIGATION OF PROTON-COUPLED ELECTRON TRANSFER IN WATER OXIDATION CATALYZED BY A RUTHENIUM COMPLEX, [Ru(tpy)(bpy)(H2 O)]2+
ar
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ERIN M. DUFFY, BRETT MARSH, JONATHAN VOSS, ETIENNE GARAND, Department of Chemistry, University of Wisconsin, Madison, WI, USA.
MI07
2+
(m=4-10) AND NiOH(H2 O)n
Pr
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PROBING SOLVATAION SHELLS OF Ni(H2 O)m
VIBRATIONAL SPECTROSCOPY.
in
The splitting of H2 O into H2 and O2 is an attractive option for alternative energy, but the oxygen evolution step poses a
significant challenge. A decades-long effort to produce a suitable water oxidation catalyst (WOC) has made progress on this
front, but the precise reaction mechanism of these catalysts is still not well understood. One of the most extensively studied
WOCs is [Ru(tpy)(bpy)(H2 O)]2+ (tpy = 2,2’:6,2”-terpyridine, bpy = 2,2’-bipyridine). Presented here are gas-phase infrared
spectra of water clusters of [Ru(tpy)(bpy)(OH2 )]2+ and the first intermediate of the catalytic cycle, [Ru(tpy)(bpy)(OH)]2+ .
In particular, the O-H stretches are used as a probe of solvation strength, and trends in their spectral shifts are examined
as a function of cluster size. With the aid of density functional theory (DFT) calculations, these spectra reveal structural
changes induced by solvation that provide clear evidence for proton-coupled electron transfer (PCET), in support of proposed
mechanisms.
+
3:07 – 3:22
(n=2-5) WITH CRYOGENIC ION
JONATHAN VOSS, BRETT MARSH, JIA ZHOU, ETIENNE GARAND, Department of Chemistry, University
of Wisconsin, Madison, WI, USA.
The solvation of metal cations, a process that dictates chemistry in both catalytic and biological systems, has been well
studied using gas-phase spectroscopy. However, until recently the solvation of cation-anion pairs has been poorly explored.
Here we present gas-phase spectra of Ni(H2 O)m 2+ (m=4-10) and NiOH(H2 O)n + (n=2-5) obtained via cryogenic ion vibrational spectroscopy (CIVS). Our results indicate that as cluster size decreases, the NiOH(H2 O)n + moiety becomes more
favorable over the Ni(H2 O)m 2+ moiety. Analysis of the spectral data in conjunction with density functional theory calculations shows that both species have a 1st solvation shell consisting of six lingands. However, the NiOH(H2 O)n + clusters
show evidence of strong interactions between a first solvation shell water ligand and the OH− group of the metal, similar to
the interactions previously observed in CaOH(H2 O)n + and MgOH(H2 O)n + .
MI08
MICROSOLVATION OF THE
(Mg2+ )2 SO4 2− (H2 O)n=4−11
Mg2 SO4
2+
CATION:
CRYOGENIC
3:24 – 3:39
VIBRATIONAL
SPECTROSCOPY
OF
PATRICK J KELLEHER, JOSEPH W DePALMA, Department of Chemistry, Yale University, New Haven, CT,
USA; CHRISTOPHER J JOHNSON, Department of Chemistry, Stony Brook University, Stony Brook, NY, USA;
JOSEPH FOURNIER, MARK JOHNSON, Department of Chemistry, Yale University, New Haven, CT, USA.
Cryogenic ion vibrational predissociation (CIVP) spectroscopy was used to examine the onset of solvation upon the
incremental addition of water molecules to the Mg2 SO4 2+ (H2 O)n cation (n = 4 – 11). D2 predissociation spectra are reported
for each cluster over the range 1000-3800 cm−1 . Initially, the Mg2+ atoms each interact with two oxygen atoms on the sulfate
anion in a bifurcated arrangement. The breaking of this motif occurs upon addition of the eighth water molecule as evidenced
by splitting of the water bend, and broad absorption in the 3000-3400 cm−1 range indicative of hydrogen bonding between
the water molecules and sulfate ion.
Intermission
63
MI09
3:58 – 4:13
CAPTURE AND STRUCTURAL DETERMINATION OF ACTIVATED INTERMEDIATES IN NICKEL CATALYZED
CO2 REDUCTION
ar
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STEPHANIE CRAIG, FABIAN MENGES, ARRON WOLK, JOSEPH FOURNIER, Department of Chemistry,
Yale University, New Haven, CT, USA; NIKLAS TÖTSCH, Physikalische Chemie II, Ruhr University Bochum,
Bochum, Germany; MARK JOHNSON, Department of Chemistry, Yale University, New Haven, CT, USA.
in
The catalyzed reduction of CO2 is an important step in the conversion of this small molecule into liquid fuels. Nickel
1,4,8,11-tetraazacyclotetradecane, Ni(cyclam), is a well-known catalyst for the reduction of CO2 in solution. Cryogenic ion
vibrational predissociation (CIVP) spectroscopy of CO2 -messenger tagged ions cooled in a temperature controlled ion trap
was used to study the starting Ni2+ (cyclam) reactant, and possible reaction intermediates and products in the gas phase.
Additionally, parental CO2 reduction was observed on the Ni(I) species [Ni(bipyridine-(NMe)2 )]2 (diphenyldiacetylene).
MI10
4:15 – 4:30
THRESHOLD IONIZATION SPECTROSCOPIC CHARACTERIZATION OF La ATOM REACTION WITH ISOPRENE
Pr
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WENJIN CAO, DONG-SHENG YANG, Department of Chemistry, University of Kentucky, Lexington, KY, USA.
The reaction between La atom and isoprene (CH2 = CHC(CH3 ) = CH2 ) was investigated in a supersonic molecular source. La(C2 H2 ), La(C3 H4 ), and La(C5 H8 ) were observed by time-of-flight mass spectrometry, and their structures and electronic states were characterized by mass-analyzed threshold ionization spectroscopy. Both La(C2 H2 ) and
La(C3 H4 ) are three-membered metallacycles formed by the C-C bond cleavage and hydrogen migration. La(C2 H2 )
has a C2v structure, whereas La(C3 H4 ) has a Cs structure. La(C5 H8 ) was identified as lanthano-methylcyclobutene
(La(CH2 C(CH3 ) = CHCH2 )) (C1 ) formed by association and double-bond migration. All three complexes have a doublet ground state with the highest occupied molecular orbital being largely a La 6s character. Ionization removes the metal
based electron, and the resultant ion has a similar structure to the neutral complex.
MI11
4:32 – 4:47
Ce-PROMOTED BOND ACTIVATION OF ETHYLENE PROBED BY MASS-ANALYZED THRESHOLD IONIZATION
SPECTROSCOPY
YUCHEN ZHANG, SUDESH KUMARI, WENJIN CAO, DONG-SHENG YANG, Department of Chemistry,
University of Kentucky, Lexington, KY, USA.
Ce(C2 H2 ) and Ce(C4 H6 ) complexes were observed in the reaction of Ce atom with ethylene in a supersonic molecular
beam source and investigated by mass-analyzed threshold ionization spectroscopy (MATI) and theoretical calculations. Preliminary data analysis shows that Ce(C2 H2 ) has a triangle structure (C2v ) with Ce binding to C2 H2 in a two-fold mode and
Ce(C4 H6 ) has a five-membered metallacyclic structure (Cs ) with Ce binding to the two terminal carbon atoms of butadiene.
The ground states of both species are triplets with a 4f1 6s1 Ce-based electron configuration and those of the corresponding
ions are doublets from the removal of the 6s1 electron. The Ce(C2 H2 ) complex is formed by ethylene dehydrogenation,
whereas Ce(C4 H6 ) by ethylene dehydrogenation and carbon-carbon bond coupling. The MATI spectra of Ce(C2 H2 ) and
Ce(C4 H6 ) are rather similar to those of the corresponding La complexes previously observed by our group, except that the
spectra of the Ce complexes exhibit two electronic transitions with almost identical vibrational intervals. This observation
suggests that the existence of a 4f electron results in an increased complexity of the electronic spectra and states of the
lanthanide hydrocarbons.
64
MI12
4:49 – 5:04
STRUCTURE DETERMINATION OF CISPLATIN-AMINO ACID ANALOGUES BY INFRARED MULTIPLE PHOTON
DISSOCIATION ACTION SPECTROSCOPY
ar
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CHENCHEN HE, XUN BAO, YANLONG ZHU, STEPHEN STROBEHN, BETT KIMUTAI, Y-W NEI, C S
CHOW, M T RODGERS, Department of Chemistry, Wayne State University, Detroit, MI, USA; JUEHAN GAO, J.
OOMENS, Institute for Molecules and Materials (IMM), Radboud University Nijmegen, Nijmegen, Netherlands.
Pr
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To gain a better understanding of the binding mechanism and assist in the optimization of relevant drug and chemical
probe design, both experimental and theoretical studies were performed on a series of amino acid-linked cisplatin derivatives,
including glycine-, lysine-, and ornithine-linked cisplatin, Gplatin, Kplatin, and Oplatin, respectively. Cisplatin, the first FDAapproved platinum-based anticancer drug, has been widely used in cancer chemotherapy. Its pharmacological mechanism has
been identified as its ability to coordinate to genomic DNA, and guanine is its major target. In previous reports, cisplatin
was successfully utilized as a chemical probe to detect solvent accessible sites in ribosomal RNA (rRNA). Among the aminoacid-linked cisplatin derivatives, Oplatin exhibits preference for adenine over guanine. The mechanism behind its different
selectivity compared to cisplatin may relate to its potential of forming a hydrogen bond between the carboxylate group in Pt
(II) complex and the 6-amino moiety of adenosine stabilizes A-Oplatin products. Tandem mass spectrometry analysis also
indicates that different coordination sites of Oplatin on adenosine affect glycosidic bond stability.
Infrared multiple photon dissociation (IRMPD) action spectroscopy experiments were performed on all three amino acidlinked cisplatin to characterize their structures. An extensive theoretical study has been performed on Gplatin to guide the
selection of the most effective theory and basis set based on its geometric information. The results for Gplatin provide the
foundation for characterization of the more complex amino acid-linked cisplatin derivatives, Oplatin and Kplatin. Structural
and energetic information elucidated for these compounds, particularly Oplatin reveal the reason for its alternative selectivity
compared to cisplatin.
MI13
5:06 – 5:21
′
STRUCTUAL EFFECTS OF CYTIDINE 2 RIBOSE MODIFICATIONS AS DETERMINED BY IRMPD ACTION SPECTROSCOPY
LUCAS HAMLOW, CHENCHEN HE, LIN FAN, RANRAN WU, BO YANG, M T RODGERS, Department of
Chemistry, Wayne State University, Detroit, MI, USA; GIEL BERDEN, J. OOMENS, Institute for Molecules and
Materials (IMM), Radboud University Nijmegen, Nijmegen, Netherlands.
Modified nucleosides, both naturally occurring and synthetic play an important role in understanding and manipulating
RNA and DNA. Naturally occurring modified nucleosides are commonly found in functionally important regions of RNA
and also affect antibiotic resistance or sensitivity. Synthetic modifications of nucleosides such as fluorinated and arabinosyl
nucleosides have found uses as anti-virals and chemotherapy agents. Understanding the effect that modifications have on
structure and glycosidic bond stability may lend insight into the functions of these modified nucleosides.
Modifications such as the naturally occurring 2′ -O-methylation and the synthetic 2′ -fluorination are believed to help
stabilize the nucleoside through the glycosidic bond stability and intramolecular hydrogen bonding. Changing the sugar
from ribose to arabinose alters the stereochemistry at the 2′ position and thus shifts the 3D orientation of the 2′ -hydroxyl
group, which also affects intramolecular hydrogen bonding and glycosidic bond stability. The structures of 2′ -deoxy-2′ fluorocytidine, 2′ -O-methylcytidine and cytosine arabinoside are examined in the current work by measuring the infrared
spectra in the IR fingerprint region using infrared multiple photon dissociation (IRMPD) action spectroscopy. The structures
accessed in the experiments were determined via comparison of the measured IRMPD action spectra to the theoretical linear
IR spectra determined by density functional theory and molecular modeling for the stable low-energy structures. Although
glycosidic bond stability cannot be quantitatively determined from this data, complementary TCID studies will establish
the effect of these modifications. Comparison of these modified nucleosides with their RNA and DNA analogues will help
elucidate differences in their intrinsic chemistry.
65
MI14
5:23 – 5:38
′
GAS-PHASE CONFORMATIONS AND ENERGETICS OF SODIUM CATIONIZED 2 -DEOXYGUANOSINE AND
GUANOSINE: IRMPD ACTION SPECTROSCOPY AND THEORETICAL STUDIES
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YANLONG ZHU, LUCAS HAMLOW, CHENCHEN HE, XUN BAO, M T RODGERS, Department of Chemistry, Wayne State University, Detroit, MI, USA; JUEHAN GAO, J. OOMENS, Institute for Molecules and Materials (IMM), Radboud University Nijmegen, Nijmegen, Netherlands.
in
In living systems, the local structures of DNA and RNA are influenced by protonation, deprotonation and noncovalent
binding interactions with cations. In order to determine the effects of Na+ cationization on the gas-phase structures of 2′ deoxyguanosine, [dGuo+Na]+ , and guanosine, [Guo+Na]+ , infrared multiple photon dissociation (IRMPD) action spectra of
these two sodium cationized DNA and RNA mononucleosides are measured over the range extending from 500 to 1850 cm−1
using the FELIX free electron laser. Complementary electronic structure calculations are performed to determine the stable
low-energy conformations of these complexes. Geometry optimizations and frequency analyses of these species are performed
at the B3LYP/6-31G* level of theory, whereas single-point energies are calculated at the B3LYP/6-311+G(2d,2p) level of
theory to determine the relative stabilities of these conformations. Comparison of the measure IRMPD action spectra and
computed linear IR spectra enable the conformations accessed in the experiments to be elucidated. In both cases, preferential
binding of the Na+ cation to O6 and N7 positions of the nucleobase is observed. Present results for the sodium cationized
nucleosides are compared to results for the analogous protonated forms of these nucleosides to elucidate the effects of multiple
chelating interactions with the sodium cation to hydrogen bonding interactions in the protonated systems on the structures
and stabilities of these nucleosides.
Pr
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MI15
UNRAVELING PROTON TRANSFER IN STEPWISE HYDRATED N-HETEROCYCLIC ANIONS
5:40 – 5:55
JOHN T. KELLY, NATHAN I HAMMER, Chemistry and Biochemistry, University of Mississippi, Oxford, MS,
USA; KIT BOWEN, Department of Chemistry, Johns Hopkins University, Baltimore, MD, USA; GREGORY S.
TSCHUMPER, Chemistry and Biochemistry, University of Mississippi, Oxford, MS, USA.
Depending upon the number and location of nitrogen atoms in a N-heterocyclic azabenzene, the addition of a single
water molecule can result in a positive electron affinity. The transfer of a proton from a solvating water azine base can be
induced by excess electron attachment. Here we explore this phenomenon through the use of photoelectron spectroscopy
and electronic structure theory. Carefully calibrated density functional theory (DFT) computations indicate that the excess
electron predominantly resides in a π* orbital of the heterocycle.
66
MJ. Small molecules
Monday, June 22, 2015 – 1:30 PM
ar
y
Chair: Leah C O’Brien, Southern Illinois University, Edwardsville, IL, USA
MJ01
1:30 – 1:45
3
3
−
DEPERTURBATION ANALYSIS FOR THE a Π AND c Σ STATES OF C2
in
JIAN TANG, WANG CHEN, KENTAROU KAWAGUCHI, Graduate School of Natural Science and Technology
, Okayama University, Okayama, Japan.
Pr
el
im
In the last symposium and a recent papera , we reported a simultaneous analysis for the Phillips and Ballik-Ramsay band
systems with a deperturbation treatment for the X1 Σ+ and b3 Σ− states of C2 and also, for the first time, the observation
of the forbidden transitions between the singlet and triplet states of C2 . In the present study, we consider the interaction
between the a3 Π and c3 Σ− states to remove some anomalies in the higher order constants of the a3 Π state presented in the
previous work. The local interaction between the a3 Π v=7 and c3 Σ− v=1 states was considered in a recent analysisb for the
perturbation of the spectrum. We consider the interaction between all the vibrational levels of the two electronic states with a
set of Dunham-like constants. The progress and results will be presented.
a
b
W. Chen, K. Kawaguchi, P. F. Bernath, and J. Tang, J. Chem. Phys. 142, 064317 (2015).
M. Nakajima and Y. Endo, J. Mol. Spectrosc. 302, 9 (2014).
MJ02
3
1:47 – 2:02
1
+
HIGH – RESOLUTION LASER SPECTROSCOPY OF THE A Π1 ← X Σ SYSTEM OF ICl IN 0.7 µm REGION.
NOBUO NISHIMIYA, TOKIO YUKIYA, MASAO SUZUKI, Faculty of Engineering, Tokyo Polytechnic University, Atsugi, Japan; ROBERT J. LE ROY, Department of Chemistry, University of Waterloo, Waterloo, ON,
Canada.
Spectroscopic data for the A 3 Π1 and X 1 Σ+ states of I35/37 Cl have been obtained by many researchers using grating
spectrometers and Fourier-transform infrared spectrometers.a,b In a previous paperc we reported the measurement of doppler
limited electronic vib-rotational absorption lines of the A 3 Π1 ← X 1 Σ+ system of I35/37 Cl using a source modulation
method, and new Mass-reduced Dunham coefficients were reported for the X-state. However, it is becoming increasingly
common to analyse diatomic molecule spectroscopic data using the “direct-potential-fit” (DPF) method in which observed
transition energies are fitted to simulated spectra generated from analyic models for the potential energy function(s). This
method tends to require fewer fitting parameters than traditional Dunham analyses, as well as having more robust extrapolation
properties in both the v and J domains. The present work combines all available previously reported data for the A 3 Π1
and X 1 Σ+ states with new measurements up to v ′ = 10 in the 0.7µm region obtained with a tone burst method using a
Ti:Sapphire Ring Laser (M Squared Ltd SolsTis CW with Tera scan) in the the first DPF analysis reported for this system.
The results of this study and our new fully analytic potential energy functions for the A 3 Π1 and X 1 Σ+ states of ICl will be
presented.
a
J.A. Coxon, R.M. Gordon and M.A. Wickramaaratchi, J. Mol. Spectr. 79 (1983) 363, 380.
H. Hedderich P.F. Bernath and G.A. McRae J. Mol. Spectr. 155 (1992) 384.
c
T.Yukiya, N. Nishimiya and M. Suzuki, J. Mol. Spectr. 269 (2011) 193.
b
67
MJ03
2:04 – 2:19
HIGH RESOLUTION LASER SPECTROSCOPY FOR ABSORPTION TO LEVELS LYING NEAR THE DISSOCIATION
LIMIT OF THE A 3 Π1 STATE OF IBr
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TOKIO YUKIYA, NOBUO NISHIMIYA, MASAO SUZUKI, Faculty of Engineering, Tokyo Polytechnic University, Atsugi, Japan; ROBERT J. LE ROY, Department of Chemistry, University of Waterloo, Waterloo, ON,
Canada.
Spectroscopic data involving levels lying near the dissociation limit are very important for determining accurate molecular well depths and full potential energy curves. In previous work, we have reported the potential functions and values of
parameters De and re for the A 3 Π1 and X 1 Σ+ states of IBr.a That study used data extending to v ′ (A) = 29 and determined
anomalous fluctuations in the v–dependence of the first differences of ∆Bv = Bv+1 − Bv for levels v ′ = 27 − 29 of the
A 3 Π1 state which, surprisingly, seems to have been smoothly accounted by a fitted potential energy function that shows no
visually perceptible irregularities. In the present work, a Ti:Sapphire ring laser(M SQUARED LASERS Ltd. SolsTiS CW
with Tera–scan) has been introduced to probe the 0.7µm region closer to the dissociation limit and examine whether the
anomalous ∆Bv behaviour expends further up the well. The results of this study will be presented.
T.Yukiya, N. Nishimiya, M. Suzuki and R.J. Le Roy, paper MG03 at the 69th International Symposium on Molecular Spectroscopy, University of Illinois (2014)
in
a
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MJ04
2:21 – 2:36
THE NEAR-INFRARED SPECTRUM OF NiCl: ANALYSES OF THE (0,1), (1,0), & (2,1) BANDS OF SYSTEM G AND
THE (1,0) BAND OF SYSTEM H
JACK C HARMS, COURTNEY N GIPSON, ETHAN M GRAMES, JAMES J O’BRIEN, Chemistry and Biochemistry, University of Missouri, St. Louis, MO, USA; LEAH C O’BRIEN, Department of Chemistry, Southern
Illinois University, Edwardsville, IL, USA.
The near-infrared spectrum of nickel chloride, NiCl, has been recorded at high resolution using intracavity laser absorption spectroscopy. The NiCl molecules were produced in a plasma discharge of a nickel hollow cathode from a trace amount
of CCl4 using Ar as the sputter gas. Spectra were collected from 12,490-12,660 cm−1 and 13,200-13,350 cm−1 as a series of
overlapping 5 cm−1 scans. The (0,1), (1,0), and (2,1) bands of the [13.0] 2 Π3/2 -X 2 Π3/2 transition, System G, were observed
at 12,537 cm−1 , 13,352 cm−1 , and 13,318 cm−1 , respectively. The (1,0) band of the [12.3] 2 Σ− -X 2 Π3/2 transition, System
H, was observed at 12,645 cm−1 . Analyses of these bands will be presented.
MJ05
2:38 – 2:53
ANALYSIS OF EMISSION SPECTRA OF YTTRIUM MONOIODIDE PRODUCED BY THE PHOTODISSOCIATION
OF YI3
WENTING WENDY CHEN, THOMAS C. GALVIN, THOMAS J. HOULAHAN, JR., J. GARY EDEN, Department of Electrical and Computer Engineering, University of Illinois at Urbana-Champaign, Urbana, IL,
USA.
Emission spectra of yttrium monoiodide (YI) spanning the 250 - 940 nm spectral region were generated by the photodissociation of yttrium tri-iodide under photoexcitation at 248 nm (KrF laser). Fluorescent spectra in the13,000 - 19,000
cm−1 and 24,000 - 40,000 cm−1 regions will be first reported. New vibrational transitions of YI in the 20,000 - 25,000 cm−1
interval will be presented as well.
68
MJ06
GENERATION OF VIBRATIONALLY EXCITED HCP FROM A STABLE SYNTHETIC PRECURSOR
2:55 – 3:05
ALEXANDER W. HULL, JUN JIANG, TREVOR J. ERICKSON, CARRIE WOMACK, MATTHEW NAVA,
CHRISTOPHER CUMMINS, ROBERT W FIELD, Department of Chemistry, MIT, Cambridge, MA, USA.
MJ07
in
Intermission
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HCP belongs to a class of reactive small molecules with much interest to spectroscopists. It bears certain similarities to
HCN, including a strong Ã(bent) - X̃(linear) ultraviolet transition, associated with the HCP-HPC isomerization pathway. HCP
has traditionally been generated by the in situ reaction of PH3 and acetylene. In this talk, we will discuss a recently developed
synthetic precursor molecule, 1,1-((triphenylphosphoranylidene)methyl)-9,10-phosphanoanthracene. At temperatures above
200 degrees Celsius, this precursor is thought to release HCP in a vibrationally excited state. We will present preliminary
spectra on this system obtained by LIF and chirped pulse millimeter wave spectroscopy.
3:24 – 3:39
1
DPF ANALYSES YIELD FULLY ANALYTIC POTENTIALS FOR THE B Πu “BARRIER” STATES OF Rb2 and Li2
AND AN IMPROVED GROUND-STATE WELL DEPTH FOR Rb2
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KAI SLAUGHTER, Department of Chemistry, University of Waterloo, Waterloo, ON, Canada; NIKESH S.
DATTANI, Graduate School of Science, Department of Chemistry, Kyoto University, Kyoto, Japan; CLAUDE S.
AMIOT, Laboratoire Aimé Cotton, CNRS, Orsay, France; AMANDA J. ROSS, UMR 5306, ILM University Lyon
1 and CNRS, Villeurbanne, France; ROBERT J. LE ROYa , Department of Chemistry, University of Waterloo,
Waterloo, ON, Canada.
Determining full model potential energy functions for molecular states that have a ‘natural’ rotationless barrier which
protrudes above the potential asymptote, such as the B 1 Πu states of alkali dimers, is a challenging problem. The present
work extends our previous Direct-Potential-Fit (DPF) analysis of data for the B 1 Πu state of Li2 b by introducing a more
sophisticated model for the long-range tail of the fully analytic ‘Double Exponential Long-Range’ (DELR) potential function
forma that takes account of the interstate coupling that occurs near the asymptotes of nS + nP alkali dimers.c This type of
analysis is then applied to data for the B 1 Πu state of Rb2 , and a concurrent extension of the DPF analysis of Seto and Le
Royd yields an improved fully analytic potential energy function for its ground X 1 Σ+
g state. The effect of taking account
of the long-range inter-state coupling on the shapes of the outer walls of the B 1 Πu state potential functions for these two
species will also be examined.
a
[email protected]
Y. Huang and R.J. Le Roy, J. Chem. Phys., 119, 7398 (2003)
c
M. Aubert-Frécon and G. Hadinger and S. Magnier and S. Rousseau, J. Mol. Spectosc., 288, 182 (1998).
d
J.Y. Seto and R.J. Le Roy, J. Chem. Phys., 113, 3067 (2000).
b
MJ08
3:41 – 3:56
LASER SPECTROSCOPY OF THE PHOTOASSOCIATION OF Rb–Ar AND Rb–Kr THERMAL PAIRS: STRUCTURE
OF THE Rb–RARE GAS A2 Π1/2 STATE NEAR THE CLASSICAL LIMIT
ANDREY E. MIRONOV, WILLIAM GOLDSHLAG, KYLE T RAYMOND, J. GARY EDEN, Department of
Electrical and Computer Engineering, University of Illinois at Urbana-Champaign, Urbana, IL, USA.
A new laser spectroscopic technique has been demonstrated for examining the structure of alkali–rare gas diatomic
electronic states near the classical limit. In two-color experiments, Rb–Ar or Rb–Kr thermal pairs are excited by free←free
or bound←free transitions while monitoring the amplified spontaneous emission produced on the Rb D1 or D2 lines. Spectra
observed lying within 10 cm−1 of the separated atom limit for the A2 Π1/2 states of Rb–Ar and Rb–Kr will be presented and
discussed.
69
MJ09
3:58 – 4:13
COLLISION-INDUCED ABSORPTION WITH EXCHANGE EFFECTS AND ANISOTROPIC INTERACTIONS: THEORY AND APPLICATION TO H2 − H2 and N2 − N2 .
ar
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TIJS KARMAN, Institute for Molecules and Materials (IMM), Radboud University Nijmegen, Nijmegen, Netherlands; EVANGELOS MILIORDOS, KATHARINE HUNT, Department of Chemistry, Michigan State University,
East Lansing, MI, USA; AD VAN DER AVOIRD, GERRIT GROENENBOOM, Institute for Molecules and Materials (IMM), Radboud University Nijmegen, Nijmegen, Netherlands.
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Collision-induced absorption spectra can be calculated quantum mechanically and from first principles. However, such
calculations are usually performed in the approximation of an isotropic interaction potential and neglecting exchange effects.
We present theory for including exchange and anisotropic interactions in the calculation of collision-induced absorption
spectra, and apply this method to the H2 − H2 and N2 − N2 systems. For H2 − H2 , the isotropic interaction approximation
is generally accurate, although significant effects of anisotropic interactions are observed in the far wing of the spectrum. For
N2 − N2 , anisotropic interactions increase the line strength at low energy by two orders of magnitude. The agreement with
experimental data is reasonable in the isotropic interaction approximation, and improves when the full anisotropic potential is
considered. The effect of the interaction anisotropy decreases at higher energy, which validates the usual isotropic interaction
approximation as a high-temperature approximation for the calculation of collision-induced absorption spectra.
MJ10
4:15 – 4:30
PHOTO-DISSOCIATION RESONANCES OF JET-COOLED NO2 AT THE DISSOCIATION THRESHOLD BY CWCRDS, CHALLENGING RRKM THEORIES
PATRICK DUPRÉ, Laboratoire de Physico-Chimie de l’Atmosphère, Université du Littoral Côte d’Opale,
Dunkerque, France.
Around 398 nm, the jet-cooled NO2 spectrum exhibits a well identified dissociation threshold (D0 ). Combining LIF
detection and continuous-wave absorption-based CRDS technique a frequency range of ∼ 25 cm−1 is analyzed at high
resolution around D0 . In addition to the usual rovibronic transitions towards long-lived energy levels, ∼ 115 wider resonances are observed. Over this energy range, the resonance widths spread from ∼ 0.006 cm−1 (∼ 450 ps) to ∼ 0.7 cm−1
(∼ 4 ps) with large fluctuations. At least two ranges of resonance width can be identified
when increasing the
¡ 2
¢ excess
¡3 energy.
¢
They are associated
with
the
opening
of
the
dissociation
channels
NO
→
NO
X
Π
,
v
=
0,
J
=
1/2
+
O
P2 and
2
1/2
¡ 2
¢
¡3 ¢
NO2 → NO X Π1/2 , v = 0, J = 3/2 + O P2 . Weighted mean unimolecular dissociation rate coefficients kuni are
calculated. The density of reactants (following the RRKM predictions) is deduced, and it will be discussed versus the density
of transitions, the density of resonances and the density of vibronic levels. The data are analyzed in the light of time-resolved
data previously reported. This analysis corroborates the existence of loose transition states along the reaction path close to
the dissociation energy in agreement with the phase space theory predictionsa .
a
[Accpeted in J. Chem. Phys.]
70
MJ11
SELF- AND CO2 -BROADENED LINE SHAPE PARAMETERS FOR THE ν2 AND ν3 BANDS OF HDO
4:32 – 4:47
ar
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V. MALATHY DEVI, D. CHRIS BENNER, Department of Physics, College of William and Mary, Williamsburg,
VA, USA; KEEYOON SUNG, LINDA BROWN, Jet Propulsion Laboratory, California Institute of Technology,
Pasadena, CA, USA; ARLAN MANTZ, Department of Physics, Astronomy and Geophysics, Connecticut College, New London, CT, USA; MARY ANN H. SMITH, Science Directorate, NASA Langley Research Center,
Hampton, VA, USA; ROBERT R. GAMACHE, Department of Environmental, Earth, and Atmospheric Sciences,
University of Massachusetts, Lowell, MA, USA; GERONIMO L. VILLANUEVA, Astrochemistry, NASA Goddard Space Flight Center, Greenbelt, MD, USA.
a
in
Knowledge of CO2 -broadened HDO widths and their temperature dependence exponents are required to interpret atmospheric spectra of Mars and Venus. We therefore used nine high-resolution, high signal-to-noise spectra of HDO and
HDO+CO2 mixtures to obtain broadening coefficients for selected transitions of the ν2 and ν3 vibrational bands located at
7.13 and 2.70 µm, respectively. The gas samples were prepared by mixing equal amounts of high-purity distilled H2 O and a
99% enriched D2 O sample. Spectra at different temperatures (255-296 K) were obtained using a 20.38 cm long coolable cella
installed in the sample compartment of the Bruker 125HR Fourier transform spectrometer at the Jet Propulsion Laboratory,
in Pasadena, CA. The retrieved parameters included accurate line positions, intensities, self- and CO2 -broadened half-width
and pressure-shift coefficients and the temperature dependences of CO2 broadened HDO. The spectroscopic parameters for
many transitions were obtained simultaneously by multispectrum fittingb of all nine spectra in each band. A non-Voigt line
shape with speed dependence was applied. Line mixing was also observed for several transition pairs. Preliminary results
will be compared to other recent measurements reported in the literature.c
K. Sung, A.W. Mantz, M.A.H. Smith, L.R. Brown, T.J. Crawford, V.M. Devi, D.C. Benner. J. Mol. Spectrosc. 162 (2010) 124-134.
D.C. Benner, C.P. Rinsland, V. Malathy Devi, M.A.H. Smith, and D. Atkins. JQSRT 53 (1995) 705-721.
Research described in this paper are performed at the College of William and Mary, Jet Propulsion Laboratory, California Institute of Technology, Connecticut College and
NASA Langley Research Center under contracts and cooperative agreements with the National Aeronautics and Space Administration.
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b
c
MJ12
DISPERSED FLUORESCENCE SPECTRA OF JET COOLED SiCN
4:49 – 5:04
MASARU FUKUSHIMA, TAKASHI ISHIWATA, Information Sciences, Hiroshima City University, Hiroshima,
Japan.
The laser induced fluorescence ( LIF ) spectrum of Ã 2 ∆ – X̃ 2 Π transition was obtained for SiCN generated by laser
ablation under supersonic free jet expansion. The vibrational structure of the dispersed fluorescence ( DF ) spectra from single
vibronic levels ( SVL’s ) was analyzed with consideration of Renner-Teller ( RT ) interaction. The usual analysis based on
the perturbation approacha , indicated considerably different spin splitting for the µ and κ levels of the X̃ 2 Π state of SiCN,
in contrast to identical spin splitting for general species based on the usual RT analysis. Further analysis of the vibrational
structure is being carried out via direct RT diagonalization.
a
J. M. Brown and F. Jørgensen, Advances in Chemical Physics 52, 117 (1983).
71
MJ13
5:06 – 5:21
1
INTERNAL FORCE FIELD DETERMINATION OF C̃ B2 STATE of SO2
JUN JIANG, BARRATT PARK, CARRIE WOMACK, ROBERT W FIELD, Department of Chemistry, MIT,
Cambridge, MA, USA.
MJ14
in
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The internal force field of C̃1 B2 state of SO2 is determined up to quartic terms. The fit incorporates observed vibrational
energy levels of both S16 O2 and S18 O2 below 3000 cm−1 , as well as rotational information of both isotopologues. With
inclusion of nine recently observed B2 symmetry levels of S16 O2 in the fit, the double-well potential in asymmetric stretching
coordinate can be better characterized. By inspecting the wavefunctions, as well as the basis state distribution of the eigenvectors, we are able to give vibrational assignments to majority of states in this energy region, based on Kellman’s semiclassical
study on fermi-resonant systems. Our analysis calls into question the validity of previous assignments of several vibrational
levels. In addition, the force field allows us to calculate Coriolis matrix elements between vibrational bands, and the calculated values agree well with experimentally derived values. In particular, it predicts and explains why the experimental values
are always much smaller than numbers predicted based on a naive harmonic picture. Our work is a first step towards a more
complete understanding of the C̃ state potential energy surface near the equilibrium geometry and it is relevant to the question
of how vibronic coupling between C̃1 B2 state and higher lying A1 state(s) gives rise to unequal S-O bond length.
5:23 – 5:38
MEASUREMENT AND MODELING OF COLD 13 CH4 SPECTRA FROM 2.1 TO 2.7 µm
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LINDA BROWN, KEEYOON SUNG, TIMOTHY J CRAWFORD, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, USA; ANDREI V. NIKITIN, SERGEY TASHKUN, Atmospheric Spectroscopy Div., Institute of Atmospheric Optics, Tomsk, Russia; MICHAEL REY, VLADIMIR TYUTEREV,
Groupe de Spectrométrie Moléculaire et Atmosphérique, UMR CNRS 7331, Université de Reims, Reims Cedex
2, France; MARY ANN H. SMITH, Science Directorate, NASA Langley Research Center, Hampton, VA, USA;
ARLAN MANTZ, Department of Physics, Astronomy and Geophysics, Connecticut College, New London, CT,
USA.
A new study of 13 CH4 line positions and intensities in the Octad region between 3600 and 4800 cm−1 will be reported.
Nine spectra were recorded with two Fourier transform spectrometers (the McMath-Pierce FTS at Kitt Peak Observatory and
the Bruker 125 HR FTS at the Jet Propulsion Laboratory) using 13 C-enriched samples at temperatures from 299 K to 80
K. Line positions and intensities were retrieved by non-linear least squares curve-fitting procedures and analyzed using the
effective Hamiltonian and the effective Dipole moment expressed in terms of irreducible tensor operators adapted to spherical
top molecules. Quantum assignments were found for all the 24 sub-vibrational states of the Octad (some as high as J=10).
Over 4750 experimental line positions and 3300 line intensities were fitted with RMS standard deviations of 0.004 cm−1 and
6.9%, respectively. A new linelist of over 9600 measured positions and intensities from 3607 to 4735 cm−1 was produced,
with known quantum assignments given for 45% of the features.a
a
Part of the research described in this paper was performed at the Jet Propulsion Laboratory, California Institute of
Technology, NASA Langley Research Center, and Connecticut College, under contracts and cooperative agreements with the
National Aeronautics and Space Administration. The support of the Groupement de Recherche International SAMIA between
CNRS (France) and RFBR (Russia) is acknowledged.
72
TA. Metal containing
Chair: Jacob Stewart, Emory University, Atlanta, GA, USA
8:30 – 8:45
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TA01
BONDING AT THE EXTREME. DETECTION AND CHARACTERIZATION OF THORIUM DIMER, Th2
TIMOTHY STEIMLEa , SETH MUSCARELLA, DAMIAN L KOKKIN, Department of Chemistry and Biochemistry, Arizona State University, Tempe, AZ, USA.
a
b
c
in
Due to the difficultly of working with actinides (radioactive, short lifetimes) and the number of electrons in these systems
our chemical understanding either experimentally or theoretically on these systems is very limited. The electronic spectrum
of thorium dimer, Th2 , is expected to be heavily congested due to the predicted twelve electronic states within an energy less
then 1 eV of the calculated 3 ∆g ground state. The chemical bond is predicted to be a quadruple bond in both the ground state
−1 b
and low lying 1 Σ+
) . Experimentally Th2 was been detected in the gas phase by mass spectrometryc .
g state (Te =400 cm
Here we report on the detection of the gas fluorescence spectrum of Th2 in the 495-560 nm range via application of 2D LIF
spectroscopy and attempts to record high resolution field free and Zeeman spectra.
NSF CHE-1265885
B.J. Roos, P.-Å. Malmqvist and L. Gagliardi, J. Am. Chem. Soc. 128, 17000-17006, 2006
M.C. Heaven, B.J. Barker and I.O. Antonov, J. Phys. Chem A. 118, 10867-10881, 2014
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TA02
8:47 – 9:02
THE QUINTESSENTIAL BOND OF MODERN SCIENCE. THE DETECTION AND CHARACTERIZATION OF DIATOMIC GOLD SULFIDE, AuS.
DAMIAN L KOKKIN, RUOHAN ZHANG, TIMOTHY STEIMLE, Department of Chemistry and Biochemistry,
Arizona State University, Tempe, AZ, USA; BRADLEY W PEARLMAN, IAN A WYSE, THOMAS D. VARBERG, Chemistry Department , Macalester College, Saint Paul, Minnesota, USA.
The gold sulfur bond is becoming ever more important to a vast range of scientific endeavors. We have recorded the
electronic spectrum of gas-phase AuS, at vibrational resolution, over the 440-740 nm wavelength range. By application of a
synergy of production techniques, hot hollow-cathode sputtering source and cold laser ablation molecular beam source, excitation from both spin components of the inverted 2 Π ground state is possible. Excitation into four different excited electronic
states involving approximately 100 red-degraded bands has been observed. The four excited states have been characterized
2 −
2
as a4 Σ1/2 , A2 Σ+
1/2 , B Σ1/2 and C ∆i . The observed red-degraded vibronic bands where then globally analyzed to determine an accurate set of term energies and vibrational constants for the excited and ground electronic states. The electronic
configurations from which these states arise will be discussed.
TA03
9:04 – 9:19
LASER SPECTROSCOPY OF RUTHENIUM CONTAINING DIATOMIC MOLECULES: RuH/D AND RuP.
ALLAN G. ADAM, RICARDA M. KONDER, NICOLE M. NICKERSON, Department of Chemistry, University
of New Brunswick, Fredericton, NB, Canada; COLAN LINTON, D. W. TOKARYK, Department of Physics,
University of New Brunswick, Fredericton, NB, Canada.
In the last few years, the Cheung group in Hong Kong and the Steimle group in Arizona have successfully studied several
ruthenium containing diatomic molecules, RuX (X =Ca , Ob , Nc , Bd ), using the laser-ablation molecular jet technique. Based
on this success, the UNB spectroscopy group decided to try and find the optical signatures of other RuX molecules. Using
CH3 OH and PH3 as reactant gases, the RuH and RuP diatomic molecules have been detected in surveys of the 420 - 675 nm
spectral region. RuD has also been made using fully deuterated methanol as a reactant. Dispersed fluorescence experiments
have been performed to determine ground state vibrational frequencies and the presence of any low-lying electronic states.
Rotationally resolved spectra for these molecules have also been taken and the analysis is proceeding. The most recent results
will be presented.
a
F. Wang et al., Journal of Chemical Physics 139, 174318 (2013).
N. Wang et al., Journal of Physical Chemistry A 117, 13279 (2013).
c
T. Steimle et al., Journal of Chemical Physics 119, 12965 (2003).
d
N. Wang et al., Chemical Physics Letters 547, 21 (2012).
b
73
TA04
OPTICAL ZEEMAN SPECTROSCOPY OF CALCIUM FLUORIDE, CaF.
9:21 – 9:36
ar
y
TIMOTHY STEIMLEa , DAMIAN L KOKKIN, Department of Chemistry and Biochemistry, Arizona State University, Tempe, AZ, USA; JACK DELVIN, MICHAEL TARBUTT, Centre for Cold Matter, Blackett Laboratory,
Imperial College London, London, United Kingdom.
Recently laser cooling has been demonstrated for the diatomic radical calcium fluoride, CaFb . The mechanism of
magneto-optical trapping for diatomic molecules has been elucidated recently by Tarbuttc where a rate model was used
to model the interaction of molecules with multiple frequencies of laser light. It was shown that the correct choice of laser
polarization depends on the sign of the upper state magnetic g-factor. The magnetic tuning of the low rotational levels in the
X 2 Σ+ , A2 Π and B 2 Σ+ electronic states of CaF, have been experimentally investigated using high resolution optical Zeeman spectroscopy of a cold molecular beam sample. The observed Zeeman-induced shifts and splittings were successfully
modeled using a traditional effective Hamiltonian approach to account for the interaction between the (ν=0) A2 Π and (ν=0)
B 2 Σ+ states. The determined magnetic g-factors for the X 2 Σ+ , A2 Π and B 2 Σ+ states are compared to those predicted by
perturbation theory.
b
c
NSF CHE-1265885
V. Zhelyazkova, A. Cournol, T.E. Wall, A. Matsushima, J.J. Hudson, E.A. Hinds, M.R. Tarbutt and B.E. Sauer, Phys. Rev. A 89, 053416 (2014)
M. R. Tarbutt, New J. Phys 17, 015007 (2015)
in
a
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TA05
ELECTRONIC TRANSITIONS OF YTTRIUM MONOPHOSPHIDE
9:38 – 9:53
ALLAN S.C. CHEUNG, Department of Chemistry, The University of Hong Kong, Hong Kong, Hong Kong;
BIU WA LI, Department of Chemistry, The Chinese University of Hong Kong, Hong Kong, Hong Kong, China;
MAN-CHOR CHAN, Department of Chemistry, The Chinese University of Hong Kong, Hong Kong, Hong Kong,
China.
Electronic transition spectrum of the yttrium monophosphide (YP) molecule in the visible region between 715 nm and
880 nm has been recorded using laser ablation/reaction free-jet expansion and laser induced fluorescence spectroscopy. The
YP molecule was produced by reacting laser - ablated yttrium atoms with PH3 seeded in argon. Thirteen vibrational bands
were analyzed and five electronic transition systems have identified, namely the [12.2] Ω = 3 - X3 Π2 transition, [13.3] Ω = 3
- X3 Π2 transition, [13.4] Ω = 3 - X3 Π2 transition, [13.5] Ω = 3 - X3 Π2 transition, and [13.4] Ω = 2 - X3 Π2 transition. Least
squares fits of the measured rotational lines yielded molecular constants for the ground and excited states. The ground state
symmetry and the bond length r0 of the YP molecule have been determined to be a X3 Π2 state and 2.4413 Å respectively in
this work. A molecular orbital energy level diagram has been used to help the assignment of the observed electronic states.
This work represents the first experimental investigation of the spectrum of the YP molecule.
TA06
9:55 – 10:10
1
1
+
1
+
1
+
ROTATIONALLY RESOLVED SPECTROSCOPY OF THE B Π ← X Σ AND C Σ ← X Σ
ELECTRONIC BANDS OF CaO
MICHAEL SULLIVAN, JACOB STEWART, MICHAEL HEAVEN, Department of Chemistry, Emory University, Atlanta, GA, USA.
The B 1 Π ← X 1 Σ+ and C 1 Σ+ ← X 1 Σ+ transitions of CaO, at energies below 30,000 cm−1 , were previously investigated by Lagerqvista . The arc source used in that work yielded spectra at energies above 30,000 cm−1 that were too congested
for analysis. In the present study we have used jet-cooling of CaO to extend the characterization of the B ← X and C ← X
band systems up to 35,000 cm−1 . Analyses of these data and spectroscopic constants will be reported. This work is being
carried out in support of two-color photoionization studies of the cation, where the higher energy vibronic levels of the B and
C states are used as the first excitation step.
a
A. Lagerqvist, Arkiv För Fysik 8, 83, 1954
Intermission
74
TA07
HIGH RESOLUTION LASER SPECTROSCOPY OF NICKEL MONOBORIDE, NiB
10:29 – 10:44
ar
y
E. S. GOUDREAU, COLAN LINTON, D. W. TOKARYK, Department of Physics, University of New Brunswick,
Fredericton, NB, Canada; ALLAN G. ADAM, Department of Chemistry, University of New Brunswick, Fredericton, NB, Canada.
Diatomic nickel boride, NiB, has been produced in the UNB laser ablation molecular jet source. Survey spectra, taken at
medium resolution with a pulsed dye laser in the 415 – 510 nm region, showed an intense band system which had previously
been observed and assigned as a 2 Π3/2 - 2 Σ+ transition by Zhen et al.a Using a single frequency ring dye laser, we have
obtained high resolution spectra of the 0-0, 2-0 and 3-0 bands of the most abundant isotopologue, 58 Ni11 B, and the 2-0 band
of 60 Ni11 B. The rotational analysis showed that the transition was from an Ω = 0.5 upper state to the ground X2 Σ+ state. The
data were found to fit equally well as 2 Σ+ - 2 Σ+ or 2 Π1/2 - 2 Σ+ . The fine structure e/f parity splitting was examined for
each of the two options in an attempt to determine the identity of the upper state. Partially resolved hyperfine structure due to
the 11 B nuclear spin, I = 3/2, was observed and analyzed to try and determine the nature of the boron atom contribution to the
ground 2 Σ+ state configuration. The results of the rotational and hyperfine structure analysis will be discussed.
J-f. Zhen, L. Wang, C-b. Qin, Q. Zhang, Y. Chen, Chinese J. Chem. Phys. 23, 626 (2010).
in
a
TA08
10:46 – 11:01
MOLECULAR LINE LISTS FOR SCANDIUM AND TITANIUM HYDRIDE USING THE DUO PROGRAM
Pr
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LORENZO LODI, Department of Physics and Astronomy, University College London, London, IX, United Kingdom; SERGEI N. YURCHENKO, Department of Physics and Astronomy, University College London, Gower
Street, London WC1E 6BT, United Kingdom; JONATHAN TENNYSON, Department of Physics and Astronomy,
University College London, London, IX, United Kingdom.
Transition-metal-containing (TMC) molecules often have very complex electronic spectra because of their large number
of low-lying, interacting electronic states, of the large multi-reference character of the electronic states and of the large
magnitude of spin-orbit and relativistic effects. As a result, fully ab initio calculations of line positions and intensities of TMC
molecules have an accuracy which is considerably worse than the one usually achievable for molecules made up by maingroup atoms only. In this presentation we report on new theoretical line lists for scandium hydride ScH and titanium hydride
TiHa . Scandium and titanium are the lightest transition metal atoms and by virtue of their small number of valence electrons
are amenable to high-level electronic-structure treatments and serve as ideal benchmark systems. We report for both systems
energy curves, dipole curves and various coupling curves (including spin-orbit) characterising their electronic spectra up to
about 20 000 cm-1. Curves were obtained using Internally-Contracted Multi Reference Configuration Interaction (IC-MRCI)
as implemented in the quantum chemistry package MOLPRO. The curves where used for the solution of the coupled-surface
ro-vibronic problem using the in-house program DUO b . DUO is a newly-developed, general program for the spectroscopy of
diatomic molecules and its main functionality will be described. The resulting line lists for ScH and TiH are made available
as part of the Exomol project c .
a
L. Lodi, S. N. Yurchenko and J. Tennyson, Mol. Phys. (Handy special issue) in press.
S. N. Yurchenko, L. Lodi, J. Tennyson and A. V. Stolyarov, Computer Phys. Comms., to be submitted.
c
J. Tennyson and S. N. Yurchenko, Mon. Not. R. Astr. Soc. 2012, 425, 21. See also www.exomol.com.
b
TA09
UV SPECTROSCOPY ON GAS PHASE Cu(I)-BIPYRIDYL COMPLEXES
11:03 – 11:18
SHUANG XU, JILA and Department of Physics, University of Colorado at Boulder, Boulder, CO, USA; CASEY
CHRISTOPHER, J. MATHIAS WEBER, JILA and the Department of Chemistry and Biochemistry, University
of Colorado-Boulder, Boulder, CO, USA.
Transition metal complexes with bipyridine ligands are of great interest in metal-organic chemistry, since they are prototypes for many applications in photochemistry and homogeneous catalysis. Under-coordinated bipyridyl complexes are
elusive species in the condensed phase, and the ligand-induced changes in electronic structure are of fundamental interest.
We present UV photodissociation spectra of mass-selected monocationic copper(I)-bipyridyl complexes [bpy-Cu-L]+ with
different ligands (L = H2 O, D2 , N2 , MeOH, Cl). Complexes were prepared via electrospray ionization of copper/bipyridine
solutions followed by accumulation and buffer gas cooling in a cryogenic Paul trap. In addition, we show spectra of similar
species based on copper oxide, [bpy-CuO-L]+ .
75
TA10
11:20 – 11:35
−
ANION PHOTOELECTRON SPECTROSCOPY OF NbW and W2
−
ar
y
D. ALEX SCHNEPPER, MELISSA A. BAUDHUIN, DOREEN LEOPOLD, Chemistry Department, University
of Minnesota, Minneapolis, MN, USA; SEAN M. CASEY, Department of Chemistry, University of Nevada, Reno,
Reno, NV, USA.
The 488 nm vibrationally-resolved photoelectron spectra of NbW− and W2 − are reported. The electron affinity of W2
( Σg + ← 2 Σu + ) is found to be 1.118 ± 0.007 eV, which differs from the value reported in a previous anion photoelectron
spectroscopic study of W2 − (1.46 eV)a , but was accurately predicted by density functional calculations (1.12 eV)b . The
fundamental vibrational frequency of W2 is measured to be 345 ± 15 cm−1 , in agreement with the value previously reported
in matrix resonance Raman studies (337 cm−1 )c . The W2 − anion is measured to have a fundamental frequency of 320
± 15 cm−1 . Several weak transitions to excited electronic states are seen and tentatively assigned based on calculated
energies. NbW has an electron affinity of 0.856 ± 0.007 eV. Vibrational frequencies are found, by Franck-Condon fitting of
overlapping transitions, to be 365 ± 20 cm−1 for NbW− and 410 ± 20 cm−1 for NbW. This increase in vibrational frequency
upon photodetachment suggests that the extra electron is in an antibonding orbital, leading to ground state assignments of 3 ∆
and 2 ∆ for the anion and neutral, respectively. These results are compared to those obtained for other Group V and Group VI
transition metal dimers and trends are discussed.
a
in
1
H. Weidele et al., Chem. Phys. Lett. 237 (1995) 425-431
Z. J. Wu, X. F. Ma, Chem. Phys. Lett. 371 (2003) 35-39
c
Z. Hu, J.-G. Dong, J. R. Lombardi, D. M. Lindsay, J. Chem. Phys. 97 (1992) 8811-8812
Pr
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b
76
TB. Mini-symposium: Accelerator-Based Spectroscopy
ar
y
Chair: Jennifer van Wijngaarden, University of Manitoba, Winnipeg, MB, Canada
TB01
INVITED TALK
8:30 – 9:00
JET-COOLED SPECTROSCOPY ON THE AILES INFRARED BEAMLINE OF THE SYNCHROTRON RADIATION
FACILITY SOLEIL
ROBERT GEORGES, IPR UMR6251, CNRS - Université Rennes 1, Rennes, France.
Pr
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The Advanced Infrared Line Exploited for Spectroscopy (AILES) extracts the bright far infrared (FIR) synchrotron
continuum of the third generation radiation facility SOLEIL. This beamline is equipped with a high resolution (10−3 cm−1 )
Bruker IFS125 Fourier transform spectrometer which can be operated in the FIR but also in the mid and near infrared by
using its internal conventional sources. The jet-AILES consortium (IPR, PhLAM, MONARIS, SOLEIL) has implemented
a supersonic-jet apparatus on the beamline to record absorption spectra at very low temperature (5-50 K) and in highly
supersaturated gaseous conditions. Heatable slit-nozzles of various lengths and widths are used to set properly the stagnation
conditions. A mechanical pumping (roots pumps) was preferred for its ability to evacuate important mass flow rates and
therefore to boost the experimental sensitivity of the set-up, the counterpart being a non-negligible consumption of both
carrier (argon, helium or nitrogen) and spectroscopic gases. Various molecular systems were investigated up to now using
the Jet-AILES apparatus. The very low temperature achieved in the gas expansion was either used to simplify the rotationvibration structure of monomers, such as SF6 a , CF4 or naphthalene b , or to stabilize the formation of weakly bonded molecular
complexes such as the trimer of HFc or the dimer of acetic acidd . The nucleation of water vapor and the nuclear spin conversion
of water were also investigated under free-jet conditions in the mid infrared.
a
High-resolution spectroscopy and analysis of the ν2 + ν3 combination band of SF6 in a supersonic jet expansion. V. Boudon, P. Asselin, P. Soulard, M. Goubet, T. R. Huet,
R. Georges, O. Pirali, P. Roy, Mol. Phys. 111, 2154–2162 (2013)
b
The far infrared spectrum of naphthalene characterized by high resolution synchrotron FTIR spectroscopy and anharmonic DFT calculations. O. Pirali, M. Goubet, T.R. Huet,
R. Georges, P. Soulard, P. Asselin, J. Courbe, P. Roy and M. Vervloet, Phys. Chem. Chem. Phys. 15, 10141-10150 (2013)
c
The cyclic ground state structure of the HF trimer revealed by far-infrared jet-cooled Fourier transform spectroscopy. P. Asselin, P. Soulard, B. Madebène, M. Goubet, T. R.
Huet, R. Georges, O. Pirali and P. Roy, Phys. Chem. Chem. Phys. 16(10), 4797-806 (2014)
d
Standard free energy of the equilibrium between the trans-monomer and the cyclic-dimer of acetic acid in the gas phase from infrared spectroscopy. M. Goubet, P. Soulard, O.
Pirali, P. Asselin, F. Réal, S. Gruet, T. R. Huet, P. Roy and R. Georges, Phys. Chem. Chem. Phys. DOI: 10.1039/c4cp05684a
TB02
LOWEST VIBRATIONAL STATES OF ACRYLONITRILE
9:05 – 9:20
ZBIGNIEW KISIEL, ON2, Institute of Physics, Polish Academy of Sciences, Warszawa, Poland; MARIE-ALINE
MARTIN-DRUMEL, Spectroscopy Lab, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA;
OLIVIER PIRALI, AILES beamline, Synchrotron SOLEIL, Saint Aubin, France.
Recent studies of the broadband rotational spectrum of acrylonitrile, H2 C=CHC≡N, revealed the presence of multiple
resonances between rotational levels in different vibrational states. The resonances affect even the ground state transitions and
their analysis allowed determination of vibrational term values for the first three excited states above the ground statea and
of vibrational energy differences in several polyads above these states.b At that time there was no infrared data of sufficient
resolution to assess the reliability of the resonance based vibrational energy determinations.
We presently report results based on a 40-700 cm−1 high-resolution spectrum of acrylonitrile recorded at the AILES
beamline of the SOLEIL synchrotron. This spectrum was reduced by using the AABS packagea,c and allowed assignment
of vibration-rotation transitions in four fundamentals, five hot bands, and one overtone band. The infrared data and previous measurements made with microwave techniques have been combined into a single global fit encompassing over 31000
measured transitions. Precise vibrational term values have been determined for the eight lowest excited vibrational states.
The new results validate the previous estimates from rotational perturbations and are also compared with results of ab initio
anharmonic force field calculations.
a
Z. Kisiel, et al., J. Mol. Spectrosc. 280 134 (2012).
A. López, et al., Astron. & Astrophys. 572, A44 (2014).
c
Z. Kisiel, et al., J. Mol. Spectrosc. 233 231 (2005).
b
77
TB03
9:22 – 9:37
FIR SYNCHROTRON SPECTROSCOPY OF HIGH TORSIONAL LEVELS OF CD3 OH: THE TAU OF METHANOL
RONALD M. LEES, LI-HONG XU, Department of Physics, University of New Brunswick, Saint John, NB,
Canada; BRANT E BILLINGHURST, EFD, Canadian Light Source Inc., Saskatoon, Saskatchewan, Canada.
Pr
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Sub-bands involving high torsional levels of the CD3 OH isotopologue of methanol have been analyzed in Fourier transform spectra recorded at the Far-Infrared beamline of the Canadian Light Source synchrotron in Saskatoon. Energy term
values for A and E torsional species of the third excited torsional state, vt = 3, are now almost complete up to rotational
levels K = 15, and thirteen substates have so far been identified for vt = 4. The spectra show interesting close groupings of
high-vt sub-bands related by Dennison’s torsional symmetry label τ , rather than A and E, that can be understood in terms of
a simple and universal free-rotor “spectral predictor” chart. Transitions between states on the same free rotor curve have torsional overlap matrix elements close to unity, so give rise to strong sub-bands providing radiative routes for rapid population
transfer through the high torsional manifold. Where the energy curves for the vt = 3 and 4 ground-state torsional levels pass
through the excited vibrational states, strong resonances can occur and a number of anharmonic and Coriolis interactions have
been detected through perturbations to the spectra and appearance of forbidden transitions due to strong mixing and intensity
borrowing.
TB04
9:39 – 9:54
FAR-INFRARED SYNCHROTRON-BASED SPECTROSCOPY OF PROTON TUNNELLING IN MALONALDEHYDE
E. S. GOUDREAU, D. W. TOKARYK, STEPHEN CARY ROSS, Department of Physics, University of New
Brunswick, Fredericton, NB, Canada.
Malonaldehyde (C3 O2 H4 ) is a prototype molecule for the study of intramolecular tunnelling proton transfer. In the
case of malonaldehyde, this transfer occurs between the two terminal oxygen atoms in its open-ring structure. Although the
ground state tunnelling splitting of 21 cm−1 has been accurately determined from microwave studiesa , the splitting has never
been obtained with high resolution in any excited vibrational state. The ν6 vibrational band was investigated in a diode laser
jet experimentb in 2004, but the researchers were not able to identify the (-) parity tunnelling component and so could not
determine the splitting. We have collected high-resolution far-IR Fourier transform spectra from a number of fundamental
vibrational bands of malonaldehyde at the CLS (Canadian Light Source) synchrotron in Saskatoon, Saskatchewan, exploiting
the considerable gain in signal-to-noise ratio at the highest resolution available afforded by the intense and well-collimated
beam. We will report on our tunnelling-rotation analysis of the anti-symmetric out-of-plane bend near 384 cm−1 and present
its tunnelling splitting value.
a
T. Baba, T. Tanaka, I. Morinoa, K. M. T. Yamada, K. Tanaka. Detection of the tunneling-rotation transitions of malonaldehyde in the submillimeter-wave region. J. Chem.
Phys., 110. 4131-4133 (1999)
b
C. Duan, D. Luckhaus. High resolution IR-diode laser jet spectroscopy of malonaldehyde. Chem. Phys. Lett., 391, 129-133 (2004)
Intermission
78
TB05
INVITED TALK
THE DISCRETE NATURE OF THE COHERENT SYNCHROTRON RADIATION
10:13 – 10:43
ar
y
STEFANO TAMMARO, AILES beam line, Synchrotron Soleil, Gif-sur-Yvette, France; OLIVIER PIRALI,
P. ROY, AILES beamline, Synchrotron SOLEIL, Saint Aubin, France; JEAN FRANÇOIS LAMPIN, GAËL
DUCOURNEAU, Institut d’Electronique de Microélectronique et de Nanotechnologie, Université de Lille 1, Villeneuve d’Ascq, France; ARNAUD CUISSET, FRANCIS HINDLE, GAËL MOURET, Laboratoire de PhysicoChimie de l’Atmosphère, Université du Littoral Côte d’Opale, Dunkerque, France.
a
in
Frequency Combs (FC) have radically changed the landscape of frequency metrology and high-resolution spectroscopy
investigations extending tremendously the achievable resolution while increasing signal to noise ratio. Initially developed in
the visible and near-IR spectral regions a , the use of FC has been expanded to mid-IR b , extreme ultra-violet c and X-ray
d
. Significant effort is presently dedicated to the generation of FC at THz frequencies. One solution based on converting
a stabilized optical frequency comb using a photoconductive terahertz emitter, remains hampered by the low available THz
power e . Another approach is based on active mode locked THz quantum-cascade-lasers providing intense FC over a relatively
limited spectral extension f . Alternatively, we show that dense powerful THz FC is generated over one decade of frequency
by coherent synchrotron radiation (CSR). In this mode, the entire ring behaves in a similar fashion to a THz resonator
wherein electron bunches emit powerful THz pulses quasi-synchronously. The observed FC has been fully characterized and
is demonstrated to be offset free. Based on these recorded specifications and a complete review of existing THz frequency
comb, a special attention will be paid onto similarities and differences between them.
Udem, Th., Holzwarth, H., Hänsch, T. W., Optical frequency metrology. Nature 416, 233-237 (2002)
Schliesser, A., Picqué, N., Hänsch, T. W., Mid-infrared frequency combs. Nature Photon. 6, 440 (2012)
Zinkstok, R. Th., Witte, S., Ubachs, W., Hogervorst, W., Eikema, K. S. E., Frequency comb laser spectroscopy in the vacuum-ultraviolet region. Physical Review A 73,
061801 (2006)
d
Cavaletto, S. M. et al. Broadband high-resolution X-ray frequency combs. Nature Photon. 8, 520-523 (2014)
e
Tani, M., Matsuura, S., Sakai, K., Nakashima, S. I., Emission characteristics of photoconductive antennas based on low-temperature-grown GaAs and semi-insulating GaAs.
Applied Optics 36, 7853-7859 (1997)
f
Burghoff, D. et al. Terahertz laser frequency combs. Nature Photon. 8, 462-467 (2014)
b
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c
TB06
10:48 – 11:03
LOW-TEMPERATURE COLLISIONAL BROADENING IN THE FAR-INFRARED CENTRIFUGAL DISTORTION
SPECTRUM OF CH4
VINCENT BOUDON, Laboratoire ICB, CNRS/Université de Bourgogne, DIJON, France; JEAN VANDER
AUWERA, Service de Chimie Quantique et Photophysique, Université Libre de Bruxelles, Brussels, Belgium;
LAURENT MANCERON, Synchrotron SOLEIL, CNRS-MONARIS UMR 8233 and Beamline AILES, Saint
Aubin, France; F. KWABIA TCHANA, LISA, CNRS, Universités Paris Est Créteil et Paris Diderot, Créteil,
France; TONY GABARD, BADR AMYAY, Laboratoire ICB, CNRS/Université de Bourgogne, DIJON, France;
MBAYE FAYE, AILES beamline, Synchrotron SOLEIL, Saint Aubin, France.
Previously, we could record on the AILES Beamline at the SOLEIL Synchrotron facility the first resolved centrifugal
distorsion spectrum of methane (CH4 ) in the THz region, which led to a precise determination of line intensities a . Later,
we could measure collisional self- and N2 -broadening coefficients at room temperatureb . This time, we reinvestigated this
topic by measuring these broadening coefficients at low temperature (between 120 K and 160 K) for J = 5 to 12, thanks to a
cryogenic multipass cellc . We used a 93 m total optical path length. Five pure methane pressures (from 10 to 100 mbar) and
four CH4 /N2 mixtures (20 % of methane with a total pressure from 100 to 800 mbar) were used. These measurements allow
us to obtain data for physical conditions approaching those of Titan’s atmosphere and to estimate temperature exponents.
a
V. Boudon, O. Pirali, P. Roy, J.-B. Brubach, L. Manceron and J. Vander Auwera, J. Quant. Spectrosc. Radiate. Transfer, 111, 1117–1129 (2010).
M. Sanzharov, J. Vander Auwera, O. Pirali, P. Roy, J.-B. Brubach, L. Manceron, T. Gabard and V. Boudon, J. Quant. Spectrosc. Radiate. Transfer, 113, 1874–1886 (2012).
c
F. Kwabia Tchana, F. Willaert, X. Landshere, J.-M. Flaud, L. Lago, M. Chapuis, C. Herbeaux, P. Roy and L. Manceron, Rev. Sci. Instrum., 84, 093101 (2013).
b
79
TB07
11:05 – 11:20
HYDROGEN AND NITROGEN BROADENED ETHANE AND PROPANE ABSORPTION CROSS SECTIONS
ar
y
ROBERT J. HARGREAVES, Department of Chemistry and Biochemistry, Old Dominion University, Norfolk,
VA, USA; DOMINIQUE APPADOO, 800 Blackburn Road, Australian Synchrotron, Melbourne, Victoria, Australia; BRANT E BILLINGHURST, EFD, Canadian Light Source Inc., Saskatoon, Saskatchewan, Canada;
PETER F. BERNATH, Department of Chemistry and Biochemistry, Old Dominion University, Norfolk, VA, USA.
Pr
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High-resolution infrared absorption cross sections are presented for the ν9 band of ethane (C2 H6 ) at 823 cm−1 . These
cross sections make use of spectra recorded at the Australian Synchrotron using a Fourier transform infrared spectrometer
with maximum resolution of 0.00096 cm−1 . The spectra have been recorded at 150, 120 and 90 K for hydrogen and nitrogen
broadened C2 H6 . They cover appropriate temperatures, pressures and broadening gases associated with the atmospheres of
the Outer Planets and Titan, and will improve atmospheric retrievals. The THz/Far-IR beamline at the Australian Synchrotron
is unique in combining a high-resolution Fourier transform spectrometer with an ‘enclosive flow cooling’ (EFC) cell designed
to study molecules at low temperatures. The EFC cell is advantageous at temperatures for which the vapor pressure is very
low, such as C2 H6 at 90 K.
Hydrogen broadened absorption cross sections of propane between 700 and 1200 cm−1 will also be presented based on
spectra obtained at the Canadian Light Source.
80
TC. Mini-symposium: Spectroscopy in the Classroom
ar
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Pr
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Chair: S. A. Cooke, Purchase College SUNY, Purchase, NY, USA
TC01
INVITED TALK
PGOPHER IN THE CLASSROOM AND THE LABORATORY
8:30 – 9:00
COLIN WESTERN, School of Chemistry, University of Bristol, Bristol, United Kingdom.
PGOPHERab
is a general purpose program for simulating and fitting rotational, vibrational and electronic spectra. As it
uses a graphical user interface the basic operation is sufficiently straightforward to make it suitable for use in undergraduate
practicals and computer based classes. This talk will present two experiments that have been in regular use by Bristol
undergraduates for some years based on the analysis of infra-red spectra of cigarette smoke and, for more advanced students,
visible and near ultra-violet spectra of a nitrogen discharge and a hydrocarbon flame. For all of these the rotational structure
is analysed and used to explore ideas of bonding. The talk will discuss the requirements for the apparatus and the support
required. Other ideas for other possible experiments and computer based exercises will also be presented, including a group
exercise.
The PGOPHER program is open source, and is available for Microsoft Windows, Apple Mac and Linux. It can be
freely downloaded from the supporting website http://pgopher.chm.bris.ac.uk. The program does not require any installation
process, so can be run on student’s own machines or easily setup on classroom or laboratory computers.
a
PGOPHER,
b
PGOPHER
a Program for Simulating Rotational, Vibrational and Electronic Structure, C. M. Western, University of Bristol, http://pgopher.chm.bris.ac.uk
version 8.0, C M Western, 2014, University of Bristol Research Data Repository, doi:10.5523/bris.huflggvpcuc1zvliqed497r2
81
TC02
SPECTROSCOPY FOR THE MASSES
9:05 – 9:20
ar
y
ROBERT J. LE ROYa , SCOTT HOPKINS, WILLIAM P. POWER, TONG LEUNG, Department of Chemistry,
University of Waterloo, Waterloo, ON, Canada; JOHN HEPBURNb , Departments of Chemistry, Physics and
Astronomy, University of British Columbia, Vancouver, BC, Canada.
in
Undergraduate students in all areas of science encounter one or more types of spectroscopy as an essential tool in their
discipline, but most never take the advanced physics or chemistry courses in which the subject is normally taught.
To address this problem, for
over
20 years our department has
V(x)
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been
teaching a popular Introducl
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l=0
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l=2
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tory Spectroscopy course that as−e
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sumes as background only a one4π ε r
term introductory chemistry course
l
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4
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5
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containing a unit on atomic the0
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ory, and a familiarity with rudifundamental
V(r) = ½ k (r−r )
vibrational
υ=5
mentary calculus.
This survey
D →
band
Rayleigh line
(Stokes)
υ=4
course
provides
an
introduction
to
υ=3
fundamental
υ=2
vibrational
Q branch
microwave, infrared, Raman, elecband
υ=1
(anti-Stokes)
pure rotation pure rotation
S branch O branch
S branch
tronic, photoelectron and NMR
S branch
Q branch
(Stokes)
(anti-Stokes)
HO
Morse
υ=0
O branch S branch
spectroscopy in a manner that alr
r→
lows students to understand many
ν
→
ν
of these phenomena as intuitive
generalizations of the problem of a particle in a 1-D box or a particle-on-a-ring, and does not require any high level mathematics.
∞
∞
r→
0
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2
n=4
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n=3
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http://leroy.uwaterloo.ca
present address: Department of Chemistry, University of British Columbia, Vancouver, BC, Canada.
TC03
9:22 – 9:37
RESEARCH AT A LIBERAL ARTS COLLEGE: MAKE SURE YOU HAVE A NET FOR YOUR HIGH WIRE ACT
MARK D. MARSHALL, HELEN O. LEUNG, Chemistry Department, Amherst College, Amherst, MA, USA.
A career as a spectroscopist at a primarily (or exclusively) undergraduate institution presents both great rewards and
significant challenges. Strategies that we have found helpful in meeting some of the challenges are presented along with
some of the work we have been able to accomplish with undergraduate students. The most important resource is a network
of colleagues who can provide mentoring and collaboration, and the role of the International Symposium on Molecular
Spectroscopy in facilitating this support is highlighted.
82
TC04
A SPECTROSCOPY BASED P-CHEM LAB, INCLUDING A DETAILED TEXT AND LAB MANUAL
9:39 – 9:54
JOHN MUENTER, Department of Chemistry, University of Rochester, Rochester, NY, USA.
in
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Rochester’s second semester physical chemistry lab course is based on spectroscopy experiments and follows a full
semester of quantum mechanics lectures. The laboratory course is fully separate from the traditional physical chemistry
course and has its own lectures. The lab course is constructed to achieve three major goals: provide a detailed knowledge
of the instrumentation that acquires data, establish a good understanding of how that data is analyzed, and give students a
familiarity with spectroscopic techniques and quantum mechanical models. Instrumentation is emphasized by using common
components to construct different experiments. Microwave, modulation and detection components are used for both OCS pure
rotation and ESR experiments. Optical components, a monochromator, and PMT detectors are used in a HeNe laser induced
fluorescence experiment on I2 (J. Chem. Ed. 73, 576 (1996)) and a photoluminescence experiment on pyrene (J. Chem. Ed.
73, 580 (1996)). OCS is studied in both the microwave and infrared regions, and the C=S stretching vibration is identified
through microwave intensity measurements. Lecture notes and laboratory instructions are combined in an exhaustive text of
more than 400 pages, containing 325 figures, 285 equations and numerous MathCad data analysis programs. This text can be
downloaded as a 10 Mbyte pdf file at chem.rochester.edu/∼muenter/CHEM232Manual.
Intermission
10:13 – 10:28
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TC05
HOW WE KNOW: SPECTROSCOPY IN THE FIRST YEAR AND BEYOND
KRISTOPHER J OOMS, Chemistry, The King’s University, Edmonton, Alberta, Canada.
Chemical educators face the never ending challenge of showing students that the content written in their textbook arises
from a rich interplay of experimentation, imagination and a desire to understand and impact the world. We have found that
asking three simple questions – What do we know, How do we know it, Why do we care – is an effective strategy to guide the
content and pedagogy within our chemistry classes. Of these three questions What we know is the most thoroughly covered
and with the growing use of rich context teaching, the Why we care is becoming more central to our chemistry teaching. How
are we doing on telling students How we know?
Spectroscopy is at the core of our ability to answer questions about how we know things about the molecular world. Yet
the teaching of spectroscopy is not a central part of student’s early chemistry learning, often being left to the later stages of
degrees and courses. For example, a brief look at common North American general chemistry text books reveals almost no
discussion of spectroscopic techniques and their centrality to understanding chemistry.
In this talk I will discuss efforts to bring spectroscopy into the first year course and some of the repercussions this has
for the whole chemistry undergraduate curriculum. The goal is to make students better aware of where the ideas in chemistry
arise from, the strengths and weaknesses of spectroscopic experiments, and how our models of the molecular world are built
on rigorous experimentation.
TC06
10:30 – 10:40
EXPANDED CHOICES FOR VIBRATION-ROTATION SPECTROSCOPY IN THE PHYSICAL CHEMISTRY TEACHING LABORATORY
JOEL R SCHMITZ, DAVID A DOLSON, Department of Chemistry, Wright State University, Dayton, OH, USA.
Many third-year physical chemistry laboratory students in the US analyze the vibration-rotation spectrum of HCl in
support of lecture concepts in quantum theory and molecular spectroscopy. Contemporary students in physical chemistry
teaching laboratories increasingly have access to FTIR spectrometers with 1/8th cm−1 resolution, which allows for expanded
choices of molecules for vibration-rotation spectroscopy. Here we present the case for choosing HBr/DBr for such a study,
where the 1/8th cm−1 resolution enables the bromine isotopic lines to be resolved. Vibration-rotation lines from the fundamental and first-overtone bands of four hydrogen bromide isotopomers are combined in a global analysis to determine
molecular spectroscopic constants. Sample production, spectral appearance, analysis and results will be presented for various
resolutions commonly available in teaching laboratories.
83
TC07
SPECTROSCOPIC CASE-BASED STUDIES IN A FLIPPED QUANTUM MECHANICS COURSE
10:42 – 10:57
STEVEN SHIPMAN, Department of Chemistry, New College of Florida, Sarasota, FL, USA.
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Students in a flipped Quantum Mechanics course were expected to apply their knowledge of spectroscopy to a variety
of case studies involving complex mixtures of chemicals. They used simulated data, prepared in advance by the instructor,
to determine the major chemical constituents of complex mixtures. Students were required to request the appropriate data in
order to ultimately make plausible guesses about the composition of the mixtures, allowing them ownership over the discovery
process. This talk will describe how these activities worked in practice, give caveats for instructors who wish to adopt them
in the future, and discuss how the results of these exercises can be used for both formative and summative assessment.
TC08
THE H-ATOM SPECTRUM: NOT A CLASSROOM DEMONSTRATION . . .
10:59 – 11:09
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WOLFGANG JÄGER, Department of Chemistry, University of Alberta, Edmonton, AB, Canada.
The spectrum of the hydrogen atom is topic of every freshmen chemistry course and at the same time a first brush with
quantum mechanics for many students. A picture of the four visible emission lines of the Balmer series is shown in probably
every introductory Chemistry textbook, but only few students have likely seen those lines with their own eyes.
I will tell you about a simple in-class activity that allows the students to see those lines and can be done in large classes
(I have done it in classes with up to 500 students) at low cost.
TC09
11:11 – 11:26
RAMAN INVESTIGATION OF TEMPERATURE PROFILES OF PHOSPHOLIPID DISPERSIONS IN THE BIOCHEMISTRY LABORATORY
NORMAN C. CRAIG, Department of Chemistry and Biochemistry, Oberlin College, Oberlin, OH, USA.
The temperature dependence of self-assembled, cell-like dispersions of phospholipids is investigated with Raman spectroscopy in the biochemistry laboratory. Vibrational modes in the hydrocarbon interiors of phospholipid bilayers are strongly
Raman active, whereas the vibrations of the polar head groups and the water matrix have little Raman activity. From Raman
spectra increases in fluidity of the hydrocarbon chains can be monitored with intensity changes as a function of temperature in
the CH-stretching region. The experiment uses detection of scattered 1064-nm laser light (Nicolet NXR module) by a Fourier
transform infrared spectrometer (Nicolet 6700). A thermoelectric heater-cooler device (Melcor) gives convenient temperature
control from 5 to 95◦ C for samples in melting point capillaries. Use of deuterium oxide instead of water as the matrix avoids
some absorption of the exciting laser light and interference with intensity observations in the CH-stretching region. Phospholipids studied range from dimyristoylphosphotidyl choline (C14 , transition T = 24◦ C) to dibehenoylphosphotidyl choline
(C22 , transition T = 74◦ C).
84
TC10
11:28 – 11:43
ONLINE AND CERTIFIABLE SPECTROSCOPY COURSES USING INFORMATION AND COMMUNICATION
TOOLS. A MODEL FOR CLASSROOMS AND BEYOND
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MANGALA SUNDER KRISHNAN, Department of Chemistry, Indian Institute of Technology Madras, Chennai
, Tamil Nadu, India.
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Online education tools and flipped (reverse) class models for teaching and learning and pedagogic and andragogic approaches to self-learning have become quite mature in the last few years because of the revolution in video, interactive
software and social learning tools. Open Educational resources of dependable quality and variety are also becoming available
throughout the world making the current era truly a renaissance period for higher education using Internet. In my presentation, I shall highlight structured course content preparation online in several areas of spectroscopy and also the design and
development of virtual lab tools and kits for studying optical spectroscopy.
Both elementary and advanced courses on molecular spectroscopy are currently under development jointly with researchers in other institutions in India. I would like to explore participation from teachers throughout the world in the
teaching-learning process using flipped class methods for topics such as experimental and theoretical microwave spectroscopy
of semi-rigid and non-rigid molecules, molecular complexes and aggregates. In addition, courses in Raman, Infrared spectroscopy experimentation and advanced electronic spectroscopy courses are also envisaged for free, online access. The National Programme on Technology Enhanced Learning (NPTEL) and the National Mission on Education through Information
and Communication Technology (NMEICT) are two large Government of India funded initiatives for producing certified and
self-learning courses with financial support for moderated discussion forums. The learning tools and interactive presentations
so developed can be used in classrooms throughout the world using flipped mode of teaching. They are very much sought
after by learners and researchers who are in other areas of learning but want to contribute to research and development through
inter-disciplinary learning. NPTEL is currently is experimenting with Massive Open Online Course (MOOC) strategy, but
with proctored and certified examination processes for large numbers in some of the above courses.
I would like to present a summary of developments in these areas to help focus classroom (online and offline) learning of
Molecular spectroscopy.
85
TD. Conformers, isomers, chirality, stereochemistry
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Chair: Emilio J. Cocinero, Universidad del Paı́s Vasco (UPV-EHU), Leioa, Spain
TD01
A JOINT THEORETICAL AND EXPERIMENTAL STUDY OF THE SiH2 OO ISOMERIC SYSTEM
8:30 – 8:45
Cambridge, MA, USA; JÜRGEN GAUSS, Institut für Physikalische Chemie, Universität Mainz, Mainz, Germany.
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In contrast to the CH2 OO isomers, those of SiH2 OO have received relatively little attention, either theoretically or
experimentally. High-level coupled cluster calculations predict a much different energy ordering in comparison to that found
for CH2 OO, with the three conformers of Si-dihydroxycarbene, HOSiOH, most stable, followed by the Si-analogues of
cis and trans formic acid, and then a cyclic isomer with C2v symmetry, c-SiH2 OO. Guided by these theoretical predictions,
rotational lines of the cis, trans isomer of HOSiOH, as well as c-SiH2 OO, have been detected by Fourier transform microwave
spectroscopy. The lines of the cyclic form are sufficiently strong that several rare isotopic species have also been found,
enabling, in combination with calculated vibrational corrections, a precise semi-experimental structure to be derived. This
talk will provide a status report on our joint study of this unusual isomeric system, and an update on searches for still other
isomers.
TD02
8:47 – 9:02
A MINTY MICROWAVE MENAGERIE: THE ROTATIONAL SPECTRA OF MENTHONE, MENTHOL, CARVACROL,
AND THYMOL
DAVID SCHMITZ, V. ALVIN SHUBERT, THOMAS BETZ, CoCoMol, Max-Planck-Institut für Struktur und
Dynamik der Materie, Hamburg, Germany; BARBARA MICHELA GIULIANO, Department of Chemistry, University of Bologna, Bologna, Italy; MELANIE SCHNELL, CoCoMol, Max-Planck-Institut für Struktur und Dynamik der Materie, Hamburg, Germany.
intensity (arb. units)
Terpenes represent one of the largest classes of secondary metabolites in nature and are derived from adding substituents
to their core building block, isoprene. They exhibit a huge assortment of structures and thus a variety of chemical and
biological activities. We recently investigated a number of monoterpenoids using broadband rotational spectroscopy in the
2-8.5 GHz frequency range.
We present a comparative study of the aromatic
monoterpenoids thymol and carvacrol and aliphatic
menthone and menthol. The differences in their
Measurement
electronic and steric structures significantly influence
molecular properties such as internal rotation barriers
and conformational flexibility. These influences are revealed in the rotational spectra. We report the rotational
spectra and the experimentally determined molecular
parameters. Results from extensive quantum chemical calculations of the conformational spaces of these
Assignment
molecules are compared with the experimentally determenthone A
menthone C
mined molecular parameters.
menthone B
4800
isomenthone-eq-ax A
5000
5200
frequency (MHz)
5400
5600
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TD03
THE ROTATIONAL SPECTRUM AND CONFORMATIONAL STRUCTURES OF METHYL VALERATE
9:04 – 9:19
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HA VINH LAM NGUYEN, CNRS et Universités Paris Est et Paris Diderot, Laboratoire Interuniversitaire des
Systèmes Atmosphériques (LISA), Créteil, France; WOLFGANG STAHL, Institute for Physical Chemistry,
RWTH Aachen University, Aachen, Germany.
Methyl valerate, C4 H9 COOCH3 , belongs to the class of fruit esters, which play an important role in nature as odorants
of different fruits, flowers, and wines. A sufficient explanation for the structure–odor relation of is not available. It is known
that predicting the odor of a substance is not possible by knowing only its chemical formula. A typical example is the
blueberry- or pine apple-like odor of ethyl isovalerate while its isomers ethyl valerate and isoamyl acetate smell like green
apple and banana, respectively. Obviously, not only the composition but also the molecular structures are not negligible
by determining the odor of a substance. Gas phase structures of fruit esters are thus important for a first step towards the
determination of structure–odor relation since the sense of smell starts from gas phase molecules.
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For this purpose, a combination of microwave spectroscopy and quantum chemical calculations (QCCs) is an excellent tool. Small esters often have sufficient vapor pressure to be transferred easily in the gas phase for a rotational study
but already contain a large number of atoms which makes them too big for classical structure determination by isotopic
substitution and requires nowadays a comparison with the structures optimized by QCCs. On the other hand, the results from
QCCs have to be validated by the experimental values.
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About the internal dynamics, the methoxy methyl group -COOCH3 of methyl acetate shows internal rotation with a
barrier of 424.581(56) cm−1 . A similar barrier height of 429.324(23) cm−1 was found in methyl propionate, where the acetyl
group is extended to the propionyl group. The investigation on methyl valerate fits well in this series of methyl alkynoates.
In this talk, the structure of the most energetic favorable conformer as well as the internal rotation shown by the methoxy
methyl group will be reported. It could be confirmed that the internal rotation barrier of the methoxy methyl group remains
by longer alkyl chain.
TD04
9:21 – 9:36
ROTATIONAL SPECTRUM OF THE METHYL SALICYLATE-WATER COMPLEX: THE MISSING CONFORMER AND
THE TUNNELING MOTIONS
SUPRIYA GHOSH, JAVIX THOMAS, YUNJIE XU, WOLFGANG JÄGER, Department of Chemistry, University of Alberta, Edmonton, AB, Canada.
Methyl salicylate is a naturally occurring organic ester produced by wintergreen and other plants. It is also found in
many over-the-counter remedies, such as muscle ache creams. The rotational spectrum of the methyl salicylate monomer was
reported previously, where the most stable, dominant conformer was identified.a The methyl salicylate-water complex was
first studied using fluorescence-detected infrared spectroscopy; only one monohydrate conformer was found in that work.b
In the present study, we employed both broadband chirped and cavity based Fourier transform microwave spectroscopy
to examine the competition between intra- and intermolecular hydrogen-bonding interactions and possible large amplitude
motions associated with the methyl group and the water subunit. In contrast to the previous infrared study, two monohydrate
conformers were identified, with carbonyl O or hydroxyl O as the hydrogen bond acceptors. Detailed analyses of the observed
hyperfine structures will be presented, as well as our efforts to extend the study to larger methyl salicylate hydration clusters.
a
b
S. Melandri, B. M. Giuliano, A. Maris, L. B. Favero, P. Ottaviani, B. Velino, W. Caminati, J. Phys. Chem. A. 2007, 111, 9076.
A. Mitsuzuka, A. Fujii, T. Ebata, N. Mikami, J. Phys. Chem. A 1998, 102, 9779.
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TD05
9:38 – 9:53
UNRAVELLING THE CONFORMATIONAL LANDSCAPE OF NICOTINOIDS: THE STRUCTURE OF COTININE BY
BROADBAND ROTATIONAL SPECTROSCOPY
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ICIAR URIARTE, PATRICIA ECIJA, EMILIO J. COCINERO, Departamento de Quı́mica Fı́sica, Universidad
del Paı́s Vasco (UPV-EHU), Bilbao, Spain; CRISTOBAL PEREZ, CoCoMol, Max-Planck-Institut für Struktur
und Dynamik der Materie, Hamburg, Germany; ELENA CABALLERO-MANCEBO, ALBERTO LESARRI,
Departamento Quı́mica Fı́sica y Quı́mica Inorgánica , Universidad de Valladolid, Valladolid, Spain.
a
J.-U. Grabow, S. Mata, J. L. Alonso, I. Peña, S. Blanco, J. C. López, C. Cabezas, Phys. Chem. Chem. Phys. 2011, 13, 21063.
A. Lesarri, E. J. Cocinero, L. Evangelisti, R. D. Suenram, W. Caminati, J.-U. Grabow, Chem. Eur. J. 2010, 16, 10214.
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Alkaloids such as nicotine, cotinine or anabasine share
a common floppy structural motif consisting of a two-ring
assembly with a 3-pyridil methylamine skeleton. In order to investigate the structure-activity relationship of these
biomolecules, structural studies with rotational resolution
have been carried out for nicotinea and anabasineb in the gas
phase, where these molecules can be probed in an “interactionfree” environment (no solvent or crystal-packing interactions).
We hereby present a structural investigation of cotinine in
a jet expansion using the chirped-pulse Fourier-transform microwave (CP-FTMW) spectrometer recently built at the University of the Basque Country (UPV-EHU). The rotational spectrum (6-18 GHz) reveals the presence of two different conformations. The conformational preferences of cotinine originate from the internal rotation of the two ring moieties, the detected
species differing in a near 180◦ rotation of pyridine. The final structure is modulated by steric effects.
TD06
9:55 – 10:10
CONFORMATIONALLY RESOLVED STRUCTURES OF JET-COOLED PHENACETIN AND ITS HYDRATED CLUSTERS
CHEOL JOO MOON, AHREUM MIN, AHREUM AHN, MYONG YONG CHOI, Department of Chemistry,
Gyeongsang National University, JinJu, GyeongsangNamDo, Korea.
Phenacetin (PA) is one of the typical synthetic fever reducers as similar to acetaminophen (AAP), a major ingredient
R
of Tylenol°.
PA and AAP are both derivatives of acetanilide (AA), substituted by ethoxyl group and hydroxyl group in
the para position of AA, respectively. In this work, we present the conformational investigations and photochemistry of
jet-cooled PA and its 1:1 hydrates using resonance enhanced multiphoton ionization (REMPI), UV-UV hole-burning and IRdip spectroscopy. Moreover, we calculated the optimized structures of PA and its 1:1 hydrates by density functional theory.
Here, we report the structural information of PA and its 1:1 hydrates with an aid of the experimental data and the ab initio
calculations.
TD07
10:12 – 10:27
CONFORMATIONAL STRUCTURES OF JET-COOLED ACETAMINOPHEN-WATER CLUSTERS BY IR-DIP SPECTROSCOPY AND COMPUTATIONAL CALCULATIONS
AHREUM MIN, AHREUM AHN, CHEOL JOO MOON, MYONG YONG CHOI, Department of Chemistry,
Gyeongsang National University, JinJu, GyeongsangNamDo, Korea.
Acetaminophen (AAP) is a widely used over-the-counter antipyretic and analgesic, a major ingredient in various cold
R
and flu drugs, Tylenol°.
In a previous study, we reported the conformational structures of jet-cooled AAP monomer by
resonance enhanced multi-photon ionization (REMPI) and UV-UV hole-burning spectroscopy in the gas phase, providing the
identification of two almost isoenergetic conformers, cis- and trans-, in the free-jet experiments. [Phys.Chem.Chem.Phys.,
2011, 13, 16537-16541]. In this talk, we like to step further on the study of AAP-water clusters via the REMPI, UV-UV
hole-burning and IR-dip spectroscopy. The conformational structures of AAP-water clusters will be compared with the
spectroscopic results and theoretical calculations.
Intermission
88
TD08
10:46 – 11:01
THE INHERENT CONFORMATIONAL PREFERENCES OF GLUTAMINE-CONTAINING PEPTIDES: THE ROLE FOR
SIDE-CHAIN BACKBONE HYDROGEN BONDS
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PATRICK S. WALSH, Department of Chemistry, Purdue University, West Lafayette, IN, USA; CARL McBURNEY, SAMUEL H. GELLMAN, Department of Chemistry, University of Wisconsin–Madison, Madison, WI,
USA; TIMOTHY S. ZWIER, Department of Chemistry, Purdue University, West Lafayette, IN, USA.
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Glutamine is widely known to be found in critical regions of peptides which readily fold into amyloid fibrils, the structures
commonly associated with Alzheimer’s disease and glutamine repeat diseases such as Huntington’s disease. Building on
previous single-conformation data on Gln-containing peptides containing an aromatic cap on the N-terminus (Z-Gln-OH
and Z-Gln-NHMe), we present here single-conformation UV and IR spectra of Ac-Gln-NHBn and Ac-Ala-Gln-NHBn, with
its C-terminal benzyl cap. These results point towards side-chain to backbone hydrogen bonds dominating the structures
observed in the cold, isolated environment of a molecular beam. We have identified and assigned three main conformers
for Ac-Gln-NHBn all involving primary side-chain to backbone interactions. Ac-Ala-Gln-NHBn extends the peptide chain
by one amino acid, but affords an improvement in the conformational flexibility. Despite this increase in the flexibility,
only a single conformation is observed in the gas-phase: a structure which makes use of both side-chain-to-backbone and
backbone-to-backbone hydrogen bonds.
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TD09
11:03 – 11:18
APPLICATIONS OF STRUCTURAL MASS SPECTROMETRY TO METABOLOMICS: CLARIFYING BOND SPECIFIC
SPECTRAL SIGNATURES WITH ISOTOPE EDITED SPECTROSCOPY
OLGA GORLOVA, CONRAD T. WOLKE, JOSEPH FOURNIER, SEAN COLVIN, MARK JOHNSON,
SCOTT MILLER, Department of Chemistry, Yale University, New Haven, CT, USA.
Comprehensive FTIR, MS/MS and NMR of pharmaceuticals are generally readily available but characterization of their
metabolites has been an obstacle. Atorvastatin is a statin drug responsible for the maintenance of cholesterol in the body.
Diovan is an angiostensin receptor antagonist used to treat high blood pressure and congestive heart failure. The field of
metabolomics, however, is struggling to obtain the identity of their structures. We implement mass spectrometry with cryogenic ion spectroscopy to study gaseous ions of the desired metabolites which, in combination, not only identify the mass of
the metabolite but also elucidate their structures through isotope-specific infrared spectroscopy.
TD10
11:20 – 11:35
ALKALI METAL-GLUCOSE INTERACTION PROBED WITH INFRARED PRE-DISSOCIATION SPECTROSCOPY
STEVEN J. KREGEL, BRETT MARSH, JIA ZHOU, ETIENNE GARAND, Department of Chemistry, The Univeristy of Wisconsin, Madison, WI, USA.
The efficient extraction of cellulose from biomass and its subsequent conversion to glucose derivatives is an attractive
goal in the field of energy science. However, current industrial methods require high ionic strength and harsh conditions.
Ionic liquids (IL’s) are a class of “green” compounds that have been shown to dissolve cellulose in concentrations of up to 25
wt%. In order to understand IL’s extraordinary cellulose dissolving power, a molecular level understanding of the IL-cellulose
interaction is needed. Toward that end, we have acquired infrared pre-dissociation spectra of M+ -glucose, where M+ =Li+ ,
Na+ , or K+ . Through comparisons with density functional theory calculations, we have determined the relative abundances
of various M+ -glucose binding motifs in both the thermodynamic and kinetic limits. These results provide insight on the
hydrogen bonding dynamics of glucose and are a step towards a fuller understanding of cellulose interactions with ionic
liquids.
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TD11
11:37 – 11:52
PROBING THE CONFORMATIONAL LANDSCAPE OF A POLYETHER BUILDING BLOCK BY RAMAN JET SPECTROSCOPY
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SEBASTIAN BOCKLITZ, MARTIN A. SUHM, Institute of Physical Chemistry, Georg-August-Universität
Göttingen, Göttingen, Germany.
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Polyethylene oxides (Polyethylene glycoles) represent a prominent class of water-soluble polymers. Surprisingly, already
1,2-dimethoxyethane as the simplest representative of this polymer family has an undetermined conformational preference in
the gas phase. Here, we address this problem by spontaneous Raman scattering in a supersonic jet.
Variation of carrier gas, stagnation pressure, nozzle distance and temperature provides information on the three lowest conformations and their mutual interconversion during collisions in the expansion. The results are compared to quantum chemical
calculations of the potential energy landscape and of normal modes.
90
TE. Instrument/Technique Demonstration
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Chair: Ken Leopold, University of Minnesota, Minneapolis, MN, USA
TE01
8:30 – 8:45
ELIMINATION OF THE VACUUM PUMP REQUIREMENT FOR HIGH-RESOLUTION ROTATIONAL SPECTROSCOPY.
JENNIFER HOLT, Department of Physics, The Ohio State University, Columbus, OH, USA; RYAN W DALY,
Battelle Memorial Institute, Columbus, Ohio, USA; CHRISTOPHER F. NEESE, FRANK C. DE LUCIA, Department of Physics, The Ohio State University, Columbus, OH, USA.
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It has been observed that with the advances being driven by the wireless communications industry, the microwave components for submillimeter wave spectrometers and sensors will become almost ”free”. Moreover, these electronic components
will require little power. However, neither of these attributes applies to the vacuum requirements for high-resolution rotational
spectroscopy. We will report on the design, construction, and operation of a simple spectroscopic cell that overcomes these
problems.
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TE02
3-D PRINTED SLIT NOZZLES FOR FOURIER TRANSFORM MICROWAVE SPECTROSCOPY
8:47 – 8:57
CHRIS DEWBERRY, BECCA MACKENZIE, Chemistry Department, University of Minnesota, Minneapolis,
MN, USA; SUSAN GREEN, Chemistry Department , Macalester College, Saint Paul, Minnesota, USA; KEN
LEOPOLD, Chemistry Department, University of Minnesota, Minneapolis, MN, USA.
3-D printing is a new technology whose applications are only beginning to be explored. In this report, we describe the
application of 3-D printing to the facile design and construction of supersonic nozzles. The efficacy of a variety of designs is
assessed by examining rotational spectra OCS and Ar-OCS using a Fourier transform microwave spectrometer with tandem
cavity and chirped-pulse capabilities. This work focuses primarily on the use of slit nozzles but other designs have been tested
as well. New nozzles can be created for $0.50 or less each, and the ease and low cost should facilitate the optimization of
nozzle performance (e.g., jet temperature or cluster size distribution) for the needs of any particular experiment.
TE03
IMPLEMENTATION OF CMOS MILLIMETER-WAVE DEVICES FOR ROTATIONAL SPECTROSCOPY
8:59 – 9:14
BRIAN DROUIN, ADRIAN TANG, ERICH T SCHLECHT, ADAM M DALY, EMILY BRAGEOT, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, USA; QUN JANE GU, YU YE, RAN SHU,
Department of Electrical and Computer Engineering, University of California - Davis, Davis, CA, USA; M.-C.
FRANK CHANG, ROD M. KIM, Electrical Engineering, University of California - Los Angeles, Los Angeles,
CA, USA.
The extension of radio-frequency CMOS circuitry into millimeter wavelengths promises the extension of spectroscopic
techniques in compact, power efficient systems. We are now exploring the use of CMOS millimeter devices for low-mass,
low-power instrumentation capable of remote or in-situ detection of gas composition during space missions. This effort
focuses on the development of a semi-confocal Fabry-Perot cavity with mm-wavelength CMOS transmitter and receiver
attached directly to a cavity coupler. Placement of the devices within the cavity structure bypasses problems encountered
with signal injection and extraction in traditional cavity designs and simultaneously takes full advantage of the miniaturized
form of the CMOS hardware. The presentation will provide an overview of the project and details of the accomplishments
thus far, including the development and testing of a pulse modulated 83-98 GHz transmitter.
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TE04
9:16 – 9:31
FAST SWEEPING DIRECT ABSORPTION (SUB)MILLIMETER SPECTROSCOPY BASED ON CHIRPED-PULSE
TECHNOLOGY
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BRIAN HAYS, Department of Chemistry, Emory University, Atlanta, GA, USA; STEVEN SHIPMAN, Department of Chemistry, New College of Florida, Sarasota, FL, USA; SUSANNA L. WIDICUS WEAVER, Department of Chemistry, Emory University, Atlanta, GA, USA.
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Chriped-pulse Fourier Transform Microwave (CP-FTMW) technology has transformed traditional microwave spectroscopy into a rapid-acquisition, broadband spectral technique. The CP-FT technique has recently been expanded to the
millimeter-wave region, but this approach requires costly equipment that is not readily available in most spectroscopy labs.
To overcome this challenge, a new experiment has been designed that combines the broadband aspects of CP-FTMW with
the high sensitivity of (sub) millimeter absorption spectroscopy. Using the arbitrary waveform generator from a CP-FTMW
experiment, and the frequency multipliers and hot electron bolometer detector from a (sub) millimeter wave experiment, we
have designed and benchmarked a highly sensitive spectrometer that offers broad spectral coverage and rapid spectral acquisition speeds. This technique is comparable in performance to other rapid-acquisition techniques currently used in the (sub)
millimeter range, but offers more sensitivity after averaging. The design of this instrument and the benchmarking results will
be presented.
TE05
9:33 – 9:48
FAST SWEEPING DOUBLE RESONANCE MICROWAVE-(SUB)MILLIMETER SPECTROSCOPY BASED ON
CHIRPED PULSE TECHNOLOGY
BRIAN HAYS, SUSANNA L. WIDICUS WEAVER, Department of Chemistry, Emory University, Atlanta, GA,
USA; STEVEN SHIPMAN, Department of Chemistry, New College of Florida, Sarasota, FL, USA.
Microwave-millimeter double resonance spectroscopy has been commonly applied by driving absorption with the millimeter light and then probing the resonance using a Fourier Transform Microwave (FTMW) spectrometer. We will present
data from an inverse scheme, in which millimeter light is used to probe a transition whose intensity is modulated by the application of microwave radiation. This detection scheme is effective in aiding the assignment of millimeter-wave transitions by
revealing which energy levels are associated with particular spectral lines. To increase the speed of this detection technique,
we incorporated an arbitrary waveform generator into the microwave source to rapidly sweep the microwave radiation through
a broad frequency range. We will discuss this approach as applied to pulsed valve experiments and in combination with a
laser-induced chemistry experiment. Potential applications to other experimental designs will also be discussed.
Intermission
92
TE06
10:07 – 10:22
ON THE PHASE DEPENDENCE OF DOUBLE-RESONANCE EXPERIMENTS IN ROTATIONAL SPECTROSCOPY
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DAVID SCHMITZ, V. ALVIN SHUBERT, ANNA KRIN, CoCoMol, Max-Planck-Institut für Struktur und Dynamik der Materie, Hamburg, Germany; DAVID PATTERSON, Department of Physics, Harvard University,
Cambridge, MA, USA; MELANIE SCHNELL, CoCoMol, Max-Planck-Institut für Struktur und Dynamik der
Materie, Hamburg, Germany.
in
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rel. phase (rad)
We report double-resonance experiments using broadband chirped-pulse Fourier transform microwave spectroscopy that
facilitate spectral assignment and yield information about weak transitions with high resolution and sensitivity. Using the
diastereomers menthone and isomenthone as examples, we investigate both the amplitude and the phase dependence of the
free-induction decay of the microwave signal transition from pumping a radio frequency transition sharing a common level.
We observe a strong phase change when scanning the radio frequency
through molecular resonance. The direction of the phase change depends on
the energy level arrangement, i.e., if it is progressive or regressive. The exπ
2
perimental results can be simulated using the density-matrix formalism using
the three-level Bloch equations and are best described with the AC Stark effect
0
within the dressed-state picture, resulting in an Autler-Townes splitting. The
simulation
π
characteristic phase inversion allows for a) the precise frequency determination
- 2
measurement
of the typically weak radio frequency transitions exploiting the high sensitivity
303.0 303.5 304.0 304.5 305.0 305.5
of the connected strong microwave signal transition and b) definitive informaRF frequency (MHz)
tion about the connectivity of the energy levels involved, i.e., progressive vs.
regressive arrangements.
TE07
10:24 – 10:39
MICROWAVE THREE-WAVE MIXING EXPERIMENTS FOR CHIRALITY DETERMINATION: CURRENT STATUS
CRISTOBAL PEREZ, V. ALVIN SHUBERT, DAVID SCHMITZ, CHRIS MEDCRAFT, ANNA KRIN,
MELANIE SCHNELL, CoCoMol, Max-Planck-Institut für Struktur und Dynamik der Materie, Hamburg, Germany.
Microwave three-wave mixing experiments have been shown to provide a novel and sensitive way to generate and measure enantiomer-specific molecular signatures. The handedness of the sample can be obtained from the phase of the molecular
free induction decay whereas the enantiomeric excess can be determined by the amplitude of the chiral signal. After the introduction of this technique by Patterson et al.a remarkable improvements have been realized and experimental strategies for
both absolute phase determination and enantiomeric excess have been presented.b,c This technique has been also successfully
implemented at higher microwave frequencies.d Here we present the current status of this technique as well future directions
and perspectives. This will be illustrated through our systematic study of chiral terpenes as well as preliminary results in
molecular clusters.
a
Patterson, D.; Schnell, M.; Doyle, J. M. Enantiomer-Specific Detection of Chiral Molecules via Microwave Spectroscopy. Nature 2013, 497, 475–477.
Patterson, D.; Doyle, J. M. Sensitive Chiral Analysis via Microwave Three-Wave Mixing. Phys. Rev. Lett. 2013, 111, 023008.
c
Shubert, V. A.; Schmitz, D.; Patterson, D.; Doyle, J. M.; Schnell, M. Identifying Enantiomers in Mixtures of Chiral Molecules with Broadband Microwave Spectroscopy.
Angew. Chem. Int. Ed. 2014, 53, 1152–1155.
d
Lobsiger, S.; Perez, C.; Evangelisti, L.; Lehmann, K. K.; Pate, B. H. Molecular Structure and Chirality Detection by Fourier Transform Microwave Spectroscopy. J. Phys.
Chem. Lett. 2014, 6, 196–200.
b
93
TE08
10:41 – 10:56
A SEMI-AUTOMATED COMBINATION OF CHIRPED-PULSE AND CAVITY FOURIER TRANSFORM MICROWAVE
SPECTROSCOPY
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KYLE N CRABTREE, Department of Chemistry, The University of California, Davis, CA, USA; MARIE-ALINE
MICHAEL C McCARTHY, Atomic and Molecular Physics, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA; SYDNEY A GASTER, TAYLOR M HALL, DEONDRE L PARKS, GORDON G BROWN,
Department of Science and Mathematics, Coker College, Hartsville, SC, USA.
in
A combination of chirped-pulse Fourier transform microwave (CP-FTMW) spectroscopy and cavity Fourier transform
microwave (c-FTMW) spectroscopy has been used to analyze the spectra of 3,4-difluorobenzaldehyde and two distinct fluoropyridine – carbon dioxide complexes. In all cases, the 8 – 18 GHz CP-FTMW spectrum was measured, and the most intense
transitions were chosen for further analysis. The intensities of the identified transitions were measured at multiple polarization
powers using the c-FTMW spectrometer. Subsequently, a series of double-resonance experiments were performed on these
transitions, again using the c-FTMW spectrometer, in order to discover which transitions shared a common quantum state.
Following the double-resonance experiments, the assignments of the spectra were trivial. The results of the spectroscopic
analysis, as well as the semi-automated method, will be presented.
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TE09
10:58 – 11:13
SUBMILLIMETER ABSORPTION SPECTROSCOPY IN SEMICONDUCTOR MANUFACTURING PLASMAS AND
COMPARISON TO THEORETICAL MODELS
YASER H. HELAL, CHRISTOPHER F. NEESE, FRANK C. DE LUCIA, Department of Physics, The Ohio State
University, Columbus, OH, USA; PAUL R. EWING, Applied Materials, Austin, TX, USA; ANKUR AGARWAL,
BARRY CRAVER, PHILLIP J. STOUT, MICHAEL D. ARMACOST, Applied Materials, Sunnyvale, CA, USA.
Plasmas used in the semiconductor manufacturing industry are of a similar nature to the environments often created for
submillimeter spectroscopic study of astrophysical species. At the low operating pressures of these plasmas, submillimeter
absorption spectroscopy is a method capable of measuring the abundances and temperatures of molecules, radicals, and ions
without disturbing any of the properties of the plasma. These measurements provide details and insight into the interactions
and reactions occurring within the plasma and their implications for semiconductor manufacturing processes. A continuous
wave, 500 to 750 GHz, absorption spectrometer was designed and used to make measurements of species in semiconductor
processing plasmas. Comparisons with expectations from theoretical plasma models provide a basis for validating and improving these models, which is a complex and difficult science itself. Furthermore, these comparisons are an evaluation for
the use of submillimeter spectroscopy as a diagnostic tool in manufacturing processes.
TE10
11:15 – 11:30
CLOUD COMPUTING FOR THE AUTOMATED ASSIGNMENT OF BROADBAND ROTATIONAL SPECTRA: PORTING AUTOFIT TO AMAZON EC2
AARON C OLINGER, STEVEN SHIPMAN, Department of Chemistry, New College of Florida, Sarasota, FL,
USA.
Recent developments in instrumentation have made it possible to collect broadband rotational spectra far faster than those
spectra can be assigned. As such, we have been working to develop automated assignment algorithms so that the analysis
can catch up with the data acquisition. The AUTOFIT programa has made strides in this direction, but it is still quite slow on
spectra with high line densities, such as those collected near room temperature. Given that the AUTOFIT algorithm is highly
parallelizable, we have used Amazon’s EC2 webservice to run a modified version of AUTOFIT simultaneously across a large
number of cores, allowing us to obtain results in a fraction of the time normally required by a typical desktop computer. In
this talk, we will describe how AUTOFIT was modified to run on EC2 and present some benchmark results.
a
Seifert, N.A., Finneran, I.A., Perez, C., Zaleski, D.P., Neill, J.L., Steber, A.L., Suenram, R.D., Lesarri, A., Shipman, S.T., Pate, B.H., J. Mol. Spec., in press
94
TF. Mini-symposium: High-Precision Spectroscopy
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Chair: Trevor Sears, Brookhaven National Laboratory, Upton, NY, USA
TF01
INVITED TALK
COMB-REFERENCED SUB-DOPPLER RESOLUTION INFRARED SPECTROMETER
1:30 – 2:00
HIROYUKI SASADA, Department of Physics, Faculty of Science and Technology, Keio University, Yokohama,
Japan.
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We have developed a sub-Doppler resolution spectrometer. A difference frequency generation source, which consists of
a pump source of a Nd:YAG laser, a signal source of an extended-cavity laser diode, and a waveguide-type PPLN, covers
from 87 to 93 THz (2900 to 3100 cm−1 ). An enhanced-cavity absorption cell remarkably improves the sensitivity of Lamb
dips. An optical frequency comb controls the central frequency of the source with an uncertainty of a few kilohertz. Because
the idler frequency is swept based on absolute frequency through the comb, recorded spectra can be repeatedly accumulated
without any frequency drift. We have applied the spectrometer to resolve the hyperfine structure of the fundamental band of
HCl with a spectral resolution of about 250 kHz.
To reduce the transit-time broadening, a novel enhanced-cavity absorption cell coupled with an idler wave of 1.9-mm
beam radius at the beam waist has been introduced. The A1 -A2 splitting of the ν1 and ν4 bands of CH3 D is resolved for a
few tens low-J transitions with the Lamb-dip linewidth of 60 to 100 kHz.
Very recently, the source linewidth has reduced to 3 kHz using a linewidth transfer technique from the Nd:YAG laser to
the extended-cavity laser diode through a novel optical frequency comb with a fast servo control. When methane sample is
cooled with liquid-nitrogen, and the beam radius is expanded to 3 mm, the observed Lamb dip is 20 kHz wide without any
enhanced-cavity absorption cell.
TF02
2:05 – 2:20
SUB-DOPPLER RESOLUTION SPECTROSCOPY OF THE FUNDAMENTAL VIBRATION BAND OF HCl WITH A
COMB-REFERENCED SPECTROMETER
KANA IWAKUNI, Department of Physics, Faculty of Science and Technology, Keio University, Yokohama,
Japan; HIDEYUKI SERA, Department of Physics, Keio University, Yokohama, IX, Japan; MASASHI ABE,
HIROYUKI SASADA, Department of Physics, Faculty of Science and Technology, Keio University, Yokohama,
Japan.
Sub-Doppler resolution spectroscopy of the fundamental bands of H35 Cl and H37 Cl has been carried out from 87
to 90 THz using a comb-referenced difference-frequency-generation (DFG) spectrometer. While the frequencies of the
pump and signal waves are locked to that of the individual nearest comb mode, the repetition rate of the comb is
varied for sweeping the idler frequency. Therefore, the relative uncertainty of the frequency scale is 10–11 , and the
spectral resolution remains about 250 kHz even when the spectrum is accumulated for a long time. The hyperfine
structures caused by chlorine nucleus are resolved for the R(0) to R(4) transitions. The figure depicts wavelengthmodulation spectrum of the R(0) transition of H35 Cl. Three Lamb dips correspond to the F= 0, 1, and –1 components left to right, and the others with arrows are cross-over resonances which are useful for determining the weak
F=–1 component frequencies for the R(1) to R(3) transitions. We have determined 49 and 44 transition frequencies
of H35 Cl and H37 Cl with an uncertainty of 10 kHz. Six molecular constants of the vibrational excited state for each
isotopomer are determined. They reproduce the determined frequencies with a standard deviation of about 10 kHz.
95
TF03
OBSERVATION AND ANALYSIS OF THE A1 -A2 SPLITTING OF CH3 D
2:22 – 2:37
MASASHI ABE, HIDEYUKI SERA, HIROYUKI SASADA, Department of Physics, Faculty of Science and
Technology, Keio University, Yokohama, Japan.
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Sub-Doppler resolution spectroscopy of CH3 D has been carried out for the ν1 and ν4 fundamental bands using a combreferenced difference-frequency generation spectrometer. Thirty transitions from the low-J ′′ and K ′′ = 3 levels are observed
with a resolution of 60 to 100 kHz, and the A1 -A2 splitting is resolved for twenty-three of the thirty transitions. Most
of them are overlapped in Doppler broadening and resolved for the first time, as far as we know. The absolute transition
frequencies are determined with a typical uncertainty of 4 kHz. The A1 -A2 splitting constant of the K ′′ = 3 levels is yielded
as 2h3,v=0 = (1.5641 ± 0.0026) Hz for the ground vibrational state. Those of the K ′ = 3 levels for the v1 = 1 states and of
the (K ′ = 2, l = −1) and (K ′ = 4, l = 1) levels for the v4 = 1 state are also determined including the J ′ -dependent terms.
TF04
2:39 – 2:54
HIGH RESOLUTION SPECTROSCOPY OF NAPHTHALENE CALIBRATED BY AN OPTICAL FREQUENCY COMB
AKIKO NISHIYAMA, KAZUKI NAKASHIMA, AYUMI MATSUBA, MASATOSHI MISONO, Applied
Physics, Fukuoka University, Fukuoka, Japan.
In high-resolution molecular spectroscopy, the precise measure of the optical frequency is crucial to evaluate minute
shifts and splittings of the energy levels. On the other hand, in such spectroscopy, thousands of spectral lines distributed over
several wavenumbers have to be measured by a continuously scanning cw laser. Therefore, the continuously changing optical
frequency of the scanning laser has to be determined with enough precision.
To satisfy these contradictory requirements, we have been developed two types of high-resolution spectroscopic systems
employing an optical frequency comb. One of the systems employs RF band-pass filters to generate equally spaced frequency
markers for optical frequency calibration, and is appropriate for wide wavelength-range measurement with relatively high
scanning rate.a In the other system, the beat frequency between the optical frequency comb and the scanning laser is controlled
by an acousto-optic frequency shifter. This system is suitable for more precise measurement, and enables detailed analyses
of frequency characteristics of scanning laser.b
In the present study, we observe Doppler-free two-photon absorption spectra of A1 B1u (v4 = 1) ← X 1 Ag (v = 0)
transition of naphthalene around 298 nm. The spectral lines are rotationally resolved and the resolution is about 100 kHz.
For q Q transition, the rotational lines are assigned, and molecular constants in the excited state are determined. In addition,
we analyze the origin of the measured linewidth and Coriolis interactions between energy levels. To determine molecular
constants more precisely, we proceed to measure and analyze spectra of other transitions, such as s S transitions.
a
A. Nishiyama, D. Ishikawa, and M. Misono, J. Opt. Soc. Am. B 30, 2107 (2013).
b
A. Nishiyama, A. Matsuba, and M. Misono, Opt. Lett. 39, 4923 (2014).
96
TF05
2:56 – 3:11
OPTICAL FREQUENCY COMB FOURIER TRANSFORM SPECTROSCOPY WITH RESOLUTION EXCEEDING THE
LIMIT SET BY THE OPTICAL PATH DIFFERENCE
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ALEKSANDRA FOLTYNOWICZ, LUCILE RUTKOWSKI, ALEXANDRA C JOHANSSSON, AMIR KHODABAKHSH, Department of Physics, Umea University, Umea, Sweden; PIOTR MASLOWSKI, GRZEGORZ
KOWZAN, Institute of Physics, Faculty of Physics, Astronomy and Informatics, Nicolaus Copernicus University, Torun, Poland; KEVIN LEE, MARTIN FERMANN, Laser Research, IMRA AMERICA, Inc, Ann Arbor, MI,
USA.
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Fourier transform spectrometers (FTS) based on optical frequency combs (OFC) allow detection of broadband molecular
spectra with high signal-to-noise ratios within acquisition times orders of magnitude shorter than traditional FTIRs based on
thermal sourcesa . Due to the pulsed nature of OFCs the interferogram consists of a series of bursts rather than a single burst at
zero optical path difference (OPD). The comb mode structure can be resolved by acquiring multiple bursts, in both mechanical
FTS systemsb and dual-comb spectroscopyc . However, in all existing demonstrations the resolution was ultimately limited
either by the maximum available OPD between the interferometer arms or by the total acquisition time enabled by the storage
memory. We present a method that provides spectral resolution exceeding the limit set by the maximum OPD using an
interferogram containing only a single burst. The method allows measurements of absorption lines narrower than the OPDlimited resolution without any influence of the instrumental lineshape function. We demonstrate this by measuring undistorted
CO2 and CO absorption lines with linewidth narrower than the OPD-limited resolution using OFC-based mechanical FTS in
the near- and mid-infrared wavelength ranges. The near-infrared system is based on an Er:fiber femtosecond laser locked to a
high finesse cavity, while the mid-infrared system is based on a Tm:fiber-laser-pumped optical parametric oscillator coupled
to a multi-pass cell. We show that the method allows acquisition of high-resolution molecular spectra with interferometer
length orders of magnitude shorter than traditional FTIR.
a
b
c
Mandon, J., G. Guelachvili, and N. Picque, Nat. Phot., 2009. 3(2): p. 99-102.
Zeitouny, M., et al., Ann. Phys., 2013. 525(6): p. 437-442.
Zolot, A.M., et al., Opt. Lett., 2012. 37(4): p. 638-640.
TF06
METROLOGY WITH AN OPTICAL FEEDBACK FREQUENCY STABILIZED CRDS
3:13 – 3:23
SAMIR KASSI, JOHANNES BURKART, UMR5588 LIPhy, Université Grenoble 1/CNRS, Saint Martin
D’heres, France.
We will present a metrological application of our recently developed Optical Feedback Frequency Stabilized - Cavity
Ring Down Spectrometer (OFFS-CRDS). This instrument, which ideally fits with an optical frequency comb for absolute
frequency calibration, relies on the robust lock of a steady cavity ring down resonator against a highly stable, radiofrequency
tuned optical source. At 1.6 µm, over 7 nm, we demonstrate Lamb dip spectroscopy of CO2 with line frequency retrieval
at the kHz level, a dynamic in excess of 700,000 on the absorption scale and a detectivity of 4x10−13 cm−1 Hz−1/2 . Such
an instrument nicely meets the requirements for the most demanding spectroscopy spanning from accurate isotopic ratio
determination and very precise lineshape recordings to Boltzmann constant redefinition.
Intermission
97
TF07
INVITED TALK
CAVITY ENHANCED ULTRAFAST TRANSIENT ABSORPTION SPECTROSCOPY
3:42 – 4:12
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THOMAS K ALLISON, Department of Chemistry, Stony Brook University, Stony Brook, NY, USA; MELANIE
ROBERTS REBER, Department of Physics and Astronomy, State University of New York, Stony Brook, NY, USA;
YUNING CHEN, Department of Chemistry, Stony Brook University, Stony Brook, NY, USA.
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Ultrafast spectroscopy on gas phase systems is typically restricted to techniques involving photoionization, whereas solution phase experiments utilize the detection of light. At Stony Brook, we are developing new techniques for performing
femtosecond time-resolved spectroscopy using frequency combs and high-finesse optical resonators. A large detection sensitivity enhancement over traditional methods enables the extension of all-optical ultrafast spectroscopies, such as broad-band
transient absorption spectroscopy (TAS) and 2D spectroscopy, to dilute gas phase samples produced in molecular beams.
Here, gas phase data can be directly compared to solution phase data. Initial demonstration experiments are focusing on the
photodissociation of iodine in small neutral argon clusters, where cluster size strongly influences the effects solvent-caging
and geminate recombination. I will discuss these initial results, our high power home-built Yb:fiber laser systems, and also
extensions of the methods to the mid-IR to study the vibrational dynamics of hydrogen bonded clusters.
TF08
NOISE-IMMUNE CAVITY-ENHANCED OPTICAL FREQUENCY COMB SPECTROSCOPY
4:17 – 4:32
LUCILE RUTKOWSKI, AMIR KHODABAKHSH, ALEXANDRA C JOHANSSSON, ALEKSANDRA
FOLTYNOWICZ, Department of Physics, Umea University, Umea, Sweden.
We present noise-immune cavity-enhanced optical frequency comb spectroscopy (NICE-OFCS), a recently developed
technique for sensitive, broadband, and high resolution spectroscopya . In NICE-OFCS an optical frequency comb (OFC) is
locked to a high finesse cavity and phase-modulated at a frequency precisely equal to (a multiple of) the cavity free spectral
range. Since each comb line and sideband is transmitted through a separate cavity mode in exactly the same way, any
residual frequency noise on the OFC relative to the cavity affects each component in an identical manner. The transmitted
intensity contains a beat signal at the modulation frequency that is immune to frequency-to-amplitude noise conversion by
the cavity, in a way similar to continuous wave noise-immune cavity-enhanced optical heterodyne molecular spectroscopy
(NICE-OHMS)b . The light transmitted through the cavity is detected with a fast-scanning Fourier-transform spectrometer
(FTS) and the NICE-OFCS signal is obtained by fast Fourier transform of the synchronously demodulated interferogram.
Our NICE-OFCS system is based on an Er:fiber femtosecond laser locked to a cavity with a finesse of ∼9000 and a
fast-scanning FTS equipped with a high-bandwidth commercial detector. We measured NICE-OFCS signals from the 3ν1 +ν3
overtone band of CO2 around 1.57 µm and achieved absorption sensitivity 6.4×10−11 cm−1 Hz−1/2 per spectral element,
corresponding to a minimum detectable CO2 concentration of 25 ppb after 330 s integration timec . We will describe the
principles of the technique and its technical implementation, and discuss the spectral lineshapes of the NICE-OFCS signals.
a
A. Khodabakhsh, C. Abd Alrahman, and A. Foltynowicz, Opt. Lett. 39, 5034-5037 (2014).
J. Ye, L. S. Ma, and J. L. Hall, J. Opt. Soc. Am. B 15, 6-15 (1998).
c
A. Khodabakhsh, A. C. Johansson, and A. Foltynowicz, Appl. Phys. B (2015) doi:10.1007/s00340-015-6010-7.
b
98
TF09
4:34 – 4:49
A NEW BROADBAND CAVITY ENHANCED FREQUENCY COMB SPECTROSCOPY TECHNIQUE USING GHz
VERNIER FILTERING.
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JÉRÔME MORVILLE, UMR 5306, ILM University Lyon 1 and CNRS, Villeurbanne, France; LUCILE
RUTKOWSKI, Department of Physics, Umea University, Umea, Sweden; GEORGI DOBREVa , Department of
Physics, Sofia University, Sofia, Bulgaria; PATRICK CROZET, UMR 5306, ILM University Lyon 1 and CNRS,
Villeurbanne, France.
a
and ILM University Lyon1
Rutkowski et al, Opt. Lett., 39(23)2014
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We present a new approach to Cavity Enhanced - Direct Frequency Comb Spectroscopy where the full emission bandwidth of a Titanium:Sapphire laser is exploited at GHz resolution. The technique is based on a low-resolution Vernier filtering
obtained with an appreciable –actively stabilized– mismatch between the cavity Free Spectral Range and the laser repetition
rate, using a diffraction grating and a split-photodiode b . This particular approach provides an immunity to frequencyamplitude noise conversion, reaching an absorption baseline noise in the 10−9 cm−1 range with a cavity finesse of only 3000.
Spectra covering 1800 cm−1√(∼ 55 THz) are acquired in recording times of about 1 second, providing an absorption figure of
merit of a few 10−11 cm−1 / Hz. Initially tested with ambient air, we report progress in using the Vernier frequency comb
method with a discharge source of small radicals.
TF10
4:51 – 5:06
A DECADE-SPANNING HIGH-RESOLUTION ASYNCHRONOUS OPTICAL SAMPLING BASED TERAHERTZ
TIME-DOMAIN SPECTROMETER
JACOB T GOOD, Division of Chemistry and Chemical Engineering, California Institute of Technology,
Pasadena, CA, USA; DANIEL HOLLAND, Translational Imaging Center, University of Southern California, Los
Angeles, CA, USA; IAN A FINNERAN, BRANDON CARROLL, MARCO A. ALLODI, GEOFFREY BLAKE,
Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA.
High-resolution ASynchronous OPtical Sampling (ASOPS) is a technique that substantially improves the combined
frequency resolution and bandwidth of ASOPS based TeraHertz Time-Domain Spectroscopy (THz-TDS) systems. We employ
two mode-locked femtosecond Ti:Sapphire oscillators with repetition frequencies of 80 MHz operating at a fixed repetition
frequency offset of 100 Hz. This offset lock is maintained by a Phase-Locked Loop (PLL) operating at the 60th harmonic of
the repetition rate of the Ti:Sapphire oscillators. Their respective time delay is scanned across 12.5 ns requiring a scan time
of 10 ms, supporting a time delay resolution of up to 15.6 fs. ASOPS-THz-TDS enables high-resolution spectroscopy that is
impossible for a THz-TDS system employing a mechanical delay stage. We measure a timing jitter of 1.36 fs for the system
using an air-gap etalon and an optical cross-correlator. We report a Root-Mean-Square deviation of 20.7 MHz and a mean
deviation of 14.4 MHz for water absorption lines from 0.5 to 2.7. High-resolution ASOPS-THz-TDS enables high resolution
spectroscopy of both gas-phase and condensed-phase samples across a decade of THz bandwidth.
99
TF11
5:08 – 5:23
DOPPLER-LIMITED SPECTROSCOPY WITH A DECADE-SPANNING TERAHERTZ FREQUENCY COMB
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IAN A FINNERAN, JACOB T GOOD, Division of Chemistry and Chemical Engineering, California Institute
of Technology, Pasadena, CA, USA; DANIEL HOLLAND, Translational Imaging Center, University of Southern California, Los Angeles, CA, USA; BRANDON CARROLL, MARCO A. ALLODI, GEOFFREY BLAKE,
Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA.
We report the generation and detection of a decade-spanning TeraHertz (THz) frequency comb (0.15-2.4 THz) using two
Ti:Sapphire femtosecond laser oscillators and ASynchronous OPtical Sampling THz Time-Domain Spectroscopy (ASOPSTHz-TDS). The measured linewidth of the comb at 1.5 THz is 3 kHz over a 60 second acquisition. With time-domain
detection of the comb, we measure three transitions of water vapor at 10 mTorr between 1-2 THz with an average Dopplerlimited fractional uncertainty of 5.9 × 10−8 . Significant improvements in bandwidth, resolution, and sensitivity are possible
with existing technologies and will enable future studies of jet-cooled hydrogen-bonded clusters.
in
TF12
5:25 – 5:40
DUAL COMB RAMAN SPECTROSCOPY ON CESIUM HYPERFINE TRANSITIONS-TOWARD A STIMULATE RAMAN SPECTRUM ON CF4 MOLECULE
TZE-WEI LIU, Taiwan International Graduate Program, Academia Sinica, Taipei, Taiwan; YEN-CHU HSU, Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei, Taiwan; WANG-YAU CHENG, Department
of Physics, National Central University, Jhongli, Taiwan.
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Raman spectroscopy is an important spectroscopic technique used in chemistry to provide a fingerprint by which
molecules can be identified. It helps us to observe vibration- rotation, and other low-frequency modes in a system. Dual
comb Raman spectroscopy allows measuring a wide bandwidth with high resolution in microseconds.
The stimulate Raman spectroscopy had been performed in early days where the nonlinear conversion efficiency depended
on laser peak power. Hence we propose an approach for rapidly resolving the Raman spectroscopy of CF4 molecule by two
Ti:sapphire comb lasers. Our progress on this proposal will be presented in the conference.
First, we have realized a compact dual Ti:sapphire comb laser systema where the dual Ti:sapphire laser system possesses
the specification of 1 GHz repetition rate. In our dual comb system, 1 GHz repetition rate, 100 kHz ∆frep and 2.4 THz
optical filter are chosen according to the demands of our future works on spectroscopy. Therefore, the maximum mode
number within free spectral range is 5*103 , and the widest range of dual-comb based spectra in that each spectrum could be
uniquely identified is 5 THz. The actual bandwidth is determined by the employed optical filter and is set to be 2.4 THz here,
so that the corresponding data acquisition time is 10 µs.
Secondly, since the identification of the tremendous spectral lines of CF4 molecule relies on a stable reference and a
reliable data-retrieving system, we propose a first-step experiment on atomic system where the direct 6S-8S 822-nm twophoton absorptionb and 8S-6P3/2 (794 nm) enhanced stimulate Raman would be realized directly by using Ti:sapphire laser.
We have successfully performed direct comb laser two-photon spectroscopy for both with and without middle-level enhanced.
For the level enhanced two-photon spectrum, our experimental setup achieves Doppler-free spectrum and a record narrow
linewidth (1 MHz).
a
b
T.-W. Liu, C.-M. Wu, Y.–C. Hsu and W.-Y. Cheng, Appl. Phys. B 117, 699 (2014)
P. Fendel, S. D. Bergeson, Th. Udem, and T. W. Hänsch, Opt. Lett. 32, 701 (2007)
100
TG. Large amplitude motions, internal rotation
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Chair: Kaori Kobayashi, University of Toyama, Toyama, Japan
TG01
1:30 – 1:45
THE BAND OF CH3 CH2 D FROM 770-880 cm
−1
in
ADAM M DALY, BRIAN DROUIN, JOHN PEARSON, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, USA; PETER GRONER, Department of Chemistry, University of Missouri - Kansas City,
Kansas City, MO, USA; KEEYOON SUNG, LINDA BROWN, Jet Propulsion Laboratory, California Institute of
Technology, Pasadena, CA, USA; ARLAN MANTZ, Department of Physics, Astronomy and Geophysics, Connecticut College, New London, CT, USA; MARY ANN H. SMITH, Science Directorate, NASA Langley Research
Center, Hampton, VA, USA.
To extend the ethane database we recorded a 0.0028 cm−1 resolution spectrum of CH3 CH2 D from 650 to 1500
cm using a Bruker IFS-125HR at the Jet Propulsion Laboratory. The 98% deuterium-enriched sample was contained in
the 0.2038 m absorption cell; one scan was taken with the sample cryogenically cooled to 130 K and another at room temperature. From the cold data, we retrieved line positions and intensities of 8704 individual absorption features from 770 –
880 cm−1 using a least squares curve fitting algorithm. From this set of measurements, we assigned 5041 transitions to the
ν17 fundamental at 805.3427686(234) cm−1 ; this band is a c-type vibration, with A and E components arising from internal
rotation. The positions were modeled using a 22 term torsional Hamiltonian using SPFIT producing the A and E energy
splitting of 5.409(25)x10−3 cm−1 (162.2(8) MHz) with a standard deviation of 7x10−4 cm−1 (21 MHz). The calculated line
intensities at 130 K agree very well with retrieved intensities. To predict line intensities at different temperatures, the partition
function value was determined at eight temperatures between 9.8 and 300 K by summing individual energy levels up to J =
99 and Ka = 99 for the six states up through ν17 at 805 cm−1 . The resulting prediction of singly-deuterated ethane absorption
at 12.5 µm enables its detection in planetary atmospheres, including those of Titan and exoplanets.
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TG02
1:47 – 2:02
LOW-TEMPERATURE HIGH-RESOLUTION INFRARED SPECTRUM OF ETHANE-1D, C2 H5 D: ROTATIONAL
ANALYSIS OF THE ν17 BAND NEAR 805 cm−1 using ERHAM.
PETER GRONER, Department of Chemistry, University of Missouri - Kansas City, Kansas City, MO, USA;
ADAM M DALY, BRIAN DROUIN, JOHN PEARSON, KEEYOON SUNG, LINDA BROWN, Jet Propulsion
Laboratory, California Institute of Technology, Pasadena, CA, USA; ARLAN MANTZ, Department of Physics,
Astronomy and Geophysics, Connecticut College, New London, CT, USA; MARY ANN H. SMITH, Science
Directorate, NASA Langley Research Center, Hampton, VA, USA.
The high-resolution infrared spectrum of gaseous ethane-d1 at 130 K shows transitions that are split into A and E components due to the interaction of overall rotation with the internal rotation of the CH3 group. An analysis of the spectrum
from 680 to 900 cm−1 with an expanded version of the program ERHAM a,b is in progress to assign the bands at E(ν17 ) = 805
cm−1 and E(ν11 ) = 715 cm−1 . A discussion of the interactions among the fundamental levels of ν17 and ν11 with overtone
levels of ν18 and the(CH3 torsion) will be given. ERHAM has been and continues to be very successful in the analysis of pure
the rotational spectra of molecules containing internal rotation and the vibrational spectrum of C2 H5 D serves as an excellent
system to test the extension of the program.
a
b
P. Groner, J. Chem. Phys. 107 4483 (1997)
P. Groner, J. Mol. Spectrosc. 278 52 (2012)
101
TG03
MICROWAVE SPECTROSCOPY OF THE EXCITED VIBRATIONAL STATES OF METHANOL
2:04 – 2:19
JOHN PEARSON, ADAM M DALY, Jet Propulsion Laboratory, California Institute of Technology, Pasadena,
CA, USA.
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Methanol is the simplest molecule with a three-fold internal rotation and the observation of its ν8 band served the primary
catalyst for the development of internal rotation theory(a,b) . The 75 subsequent years of investigation into the ν8 band region
have yielded a large number assignments, numerous high precision energy levels and a great deal of insight into the coupling of
νt =3 & 4 with ν8 , ν7 , ν11 and other nearby states(c) . In spite of this progress numerous assignment mysteries persist, the origin
of almost half the far infrared laser lines remain unknown and all attempts to model the region quantum mechanically have
had very limited success. The C3V internal rotation Hamiltonian has successfully modeled the νt =0,1 & 2 states of methanol
and other internal rotors(d) . However, successful modeling of the coupling between torsional bath states and excited small
amplitude motion remains problematic and coupling of multiple interacting excited small amplitude vibrations featuring large
amplitude motions remains almost completely unexplored. Before such modeling can be attempted, identifying the remaining
low lying levels of ν7 and ν11 is necessary. We present an investigation into the microwave spectrum of ν7 , ν8 and ν11 along
with the underlying torsional bath states in νt =3 and νt = 4.
(a)
A. Borden, E.F. Barker J. Chem. Phys., 6, 553 (1938).
(b)
J. S. Koehler and D. M. Dennison, Phys. Rev. 57, 1006 (1940).
(c)
R. M. Lees, Li-Hong Xu, J. W. C. Johns, B. P. Winnewisser, and M. Lock, J. Mol. Spectrosc. 243, 168 (2007).
(d)
L.-H. Xu, J. Fisher, R.M. Lees, H.Y. Shi, J.T. Hougen, J.C. Pearson, B.J. Drouin, G.A. Blake, R. Braakman J. Mol.
Spectrosc., 251, 305 (2008).
TG04
FIRST HIGH RESOLUTION ANALYSIS OF THE ν21 BAND OF PROPANE AT 921.4 cm
AMPLITUDE-MOTION TUNNELLING EFFECTS
2:21 – 2:36
−1
: EVIDENCE OF LARGE-
AGNES PERRIN, F. KWABIA TCHANA, JEAN-MARIE FLAUD, LISA, CNRS, Universités Paris Est Créteil
et Paris Diderot, Créteil, France; LAURENT MANCERON, Synchrotron SOLEIL, CNRS-MONARIS UMR 8233
and Beamline AILES, Saint Aubin, France; JEAN DEMAISON, NATALJA VOGT, Section of Chemical Information Systems, Universität Ulm, Ulm, Germany; PETER GRONER, Department of Chemistry, University of
Missouri - Kansas City, Kansas City, MO, USA; WALTER LAFFERTY, Optical Technology Division, National
Institute of Standards and Technology, Gaithersburg, MD, USA.
A high resolution (0.0015 cm−1 ) IR spectrum of propane, C3 H8 , has been recorded with synchrotron radiation at the
French light source facility at SOLEIL coupled to a Bruker IFS-125 Fourier transform spectrometer. A preliminary analysis
of the ν21 fundamental band (B1 , CH3 rock) near 921.4 cm−1 reveals that the rotational energy levels of 211 are split by
interactions with the internal rotations of the methyl groups. Conventional analysis of this A-type band yielded band centers
at 921.3724(38), 921.3821(33) and 921.3913(44) cm−1 for the AA, EE and AE + EA tunneling splitting components,
respectively.a These torsional splittings most probably are due to anharmonic and/or Coriolis resonance coupling with nearby
highly excited states of both internal rotations of the methyl groups. In addition, several vibrational-rotational resonances
were observed that affect the torsional components in different ways. The analysis of the B-type band near 870 cm−1 (ν8 ,
sym. C-C stretch) which also contains split rovibrational transitions due to internal rotation is in progress. It is performed
by using the effective rotational Hamiltonian method ERHAMb with a code that allows prediction and least-squares fitting of
such vibration-rotation spectra.
a
b
A. Perrin et al., submitted to J.M ol.Spectrosc.
P Groner, J.Chem.P hys. 107 (1997) 4483; J.M ol.Spectrosc. 278 (2012) 52.
102
TG05
2:38 – 2:53
TORSIONAL STRUCTURE IN THE Ã − X̃ SPECTRUM OF THE CH3 O2 AND CH2 XO2 RADICALS
MENG HUANG, ANNE B McCOY, TERRY A. MILLER, Department of Chemistry and Biochemistry, The Ohio
State University, Columbus, OH, USA.
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Large amplitude motions in methyl rotor systems have been well studied, especially the coupling between the CH3
torsion and the CH stretches. The CH3 OO radical is a example of a system where this coupling is relatively small, but its
effects still can be observed in the the infrared spectrum taken by the Lee group.a Rotational contour simulations based on
an asymmetric rotor model show good agreement with the experimental spectrum except for an unexplained broadening of
the Q-branch of one of the CH stretch features. The broadening is likely caused by low frequency torsional modes populated
at room temperature resulting in sequence band transitions that are slightly shifted from the origin. A reduced dimension
model involving the three CH stretches and the CH3 torsion is applied to CH3 OO to simulate the observed spectrum. The
CH stretches are described by a harmonically coupled anharmonic oscillator model in which the parameters depend on the
CH3 torsion angle. Based on these calculations, the observed broadening of the Q-branch can be qualitatively explained by
coupling between two CH stretch/CH3 torsion combination bands which differ by one quantum in torsional excitation. The
Ã-X̃ electronic transitions of halogenated methyl peroxy radicals, CH2 XOO (X-Cl, Br, I), show a complementary structure.
At room temperature multiple peaks have been observed in the region of the origin and OO stretch vibronic bands in all three
radicals with the spectra for CH2 IO2 being by far the most complex. This structure may again be the result of hot bands
originating from excited torsional levels. Several theoretical models have been investigated to calculate the Franck-Condon
factors that govern the structure. A calculation that models the I-C-O-O torsion using curvilinear internal coordinates and
molecular geometry and harmonic torsion frequencies predicted by electronic structure calculations shows the best agreement
between the CH2 IOO experimental and simulated spectra. The multiple peak structure results from the change in X-CO-O torsion dihedral between the X̃ state and Ã states. Interestingly, a similar calculation with Cartesian displacement
coordinates fails to explain the torsional structure. This study shows the importance of coordinate system choice if a significant
displacement in the torsional coordinate occurs upon electronic excitation.
a
K.-H. Hsu, Y.-P. Lee, M. Huang, T. A. Miller, TD08, 68th International Symposium of Molecular Spectroscopy (2013)
TG06
2:55 – 3:10
UPDATE OF THE ANALYSIS OF THE PURE ROTATIONAL SPECTRUM OF EXCITED VIBRATIONS OF CH3 CH2 CN
ADAM M DALY, JOHN PEARSON, SHANSHAN YU, BRIAN DROUIN, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, USA; CELINA BERMÚDEZ, JOSÉ L. ALONSO, Grupo de Espectroscopia Molecular, Lab. de Espectroscopia y Bioespectroscopia, Unidad Asociada CSIC, Universidad de
Valladolid, Valladolid, Spain.
The torsion-vibration-rotation analysis of nearly degenerate vibrational states involving both small and large amplitude
motion has escaped satisfactory quantum mechanical description. Unfortunately the interstellar medium is filled with many
prevalent molecules that feature internal rotation that couples strongly with torsional bath states. Many excited states are
observed in emission in hot cores associated with massive star formation and it is likely that absorption in the infrared will
be seen by JWST. We present our progress on the analysis of the high resolution pure rotational spectrum of ethyl cyanide,
CH3 CH2 CN, which is highly abundant in hot cores with massive star formation and can serve as a sensitive temperature and
source size probea . Although the ground state has been assigned to 1.6 THzb , the two vibrational states ν13 and ν21 , the
C-C-N bend and torsion, have only been assigned up to 400 GHzc . It is clear that detailed understanding of excited states
will help properly model the temperature dependence of the intensity. We will report the progress on the fit up to 1.5 THz for
the states ν13 , ν21 , ν20 and ν12 , at 206.5 cm−1 , 212 cm−1 , 375 cm−1 and 532 cm−1 respectively. In spite of a nearly 1200
cm−1 barrier to internal rotation all the vibrational states observed feature A/E splittings inconsistent with such a high barrier
suggesting that there is extensive coupling between the torsional bath states and the excited vibrations. The low lying states
of ethyl cyanide provide an opportunity to assess all the possible interaction under the CS group for both A and E symmetry
in the high barrier case to serve as a benchmark for developing theory for the analysis of lower barrier cases.
a
A.M. Daly, C. Bermúdez, A. López, B. Tercero, J.C. Pearson, N. Marcelino, J.L. Alonso, J. Cernicharo Astrophys. J., 768 81 (2013)
C.S. Brauer, J.C. Pearson, B.J. Drouin, S. Yu ApJ Suppl. Ser., 184 133 (2009)
c
D.M. Mehringer, J.C. Pearson, J. Keene, T.G. Phillips Astrophys. J., 608 306 (2004)
b
Intermission
103
TG07
UNUSUAL INTERNAL ROTATION COUPLING IN THE MICROWAVE SPECTRUM OF PINACOLONE
3:29 – 3:44
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YUEYUE ZHAO, Institute for Physical Chemistry, RWTH Aachen University, Aachen, Germany; HA VINH
LAM NGUYEN, CNRS et Universités Paris Est et Paris Diderot, Laboratoire Interuniversitaire des Systèmes
Atmosphériques (LISA), Créteil, France; WOLFGANG STAHL, Institute for Physical Chemistry, RWTH Aachen
University, Aachen, Germany; JON T. HOUGEN, Sensor Science Division, National Institute of Standards and
Technology, Gaithersburg, MD, USA.
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The molecular-beam Fourier-transform microwave spectrum of pinacolone (methyl tert-butyl ketone) has been measured
in several regions between 2 and 40 GHz. Assignments of a large number of A and E transitions were confirmed by combination differences, but fits of the assigned spectrum using several torsion-rotation computer programs based on different models
led to the unexpected conclusion that no existing program correctly captures the internal dynamics of this molecule. A second
puzzle arose when it became clear that roughly half of the spectrum remained unassigned even after all predicted transitions
were added to the assignment list. Quantum chemical calculations carried out at the MP2/6-311++G(d,p) level indicate that
this molecule does not have a plane of symmetry at equilibrium, and that internal rotation of the light methyl group induces
a large oscillatory motion of the heavy tert-butyl group from one side of the Cs saddle point to the other. The effect of this
non-Cs equilibrium structure was modeled for J = 0 levels by a simple two-top torsional Hamiltonian, where magnitudes of
the strong top-top coupling terms were determined directly from the ab initio two-dimensional potential surface. A plot of
the resultant torsional levels on the same scale as a one-dimensional potential curve along the zig-zag path connecting the six
(unequally spaced) minima bears a striking resemblance to the 1:2:1 splitting pattern of levels in an internal rotation problem
with a six-fold barrier. A plot of the six minima closely resembles the potential surface for methylamine. This talk will focus
on implications of these resemblances for future work.
TG08
THE COMPLETE ROTATIONAL SPECTRUM OF CH3 NCO UP TO 376 GHz
3:46 – 4:01
ZBIGNIEW KISIEL, ON2, Institute of Physics, Polish Academy of Sciences, Warszawa, Poland; LUCIE
KOLESNIKOVÁ, JOSÉ L. ALONSO, Grupo de Espectroscopia Molecular, Lab. de Espectroscopia y Bioespectroscopia, Unidad Asociada CSIC, Universidad de Valladolid, Valladolid, Spain; IVAN MEDVEDEV,
Department of Physics, Wright State University, Dayton, OH, USA; SARAH FORTMAN, MANFRED WINNEWISSER, FRANK C. DE LUCIA, Department of Physics, The Ohio State University, Columbus, OH, USA.
The methylisocyanate molecule, CH3 NCO, is of interest as a potential astrophysical species and as a model system
for the study of quasisymmetric behavior. The rotational spectrum is made very complex by the presence in CH3 NCO of
two large-amplitude motions: an almost free internal rotation and a low barrier skeletal bending motion. This challenging
spectrum has, nevertheless, been assigned at 8-38 GHz by Stark spectroscopya and has been measured at 117-376 GHz with
the broadband FASSST technique.b
We presently report the results of measuring this spectrum also in supersonic expansion for the transitions below 40 GHz,
and at room-temperature in the region between 40 and 120 GHz. In this way we are finally able to confirm the assignment
of the ground state and of the internal rotation m=1 state and to analyse the nitrogen hyperfine splitting structure. It is also
possible to confidently transfer the Stark-based assignment to the transition sequences measured in the mm-wave region, and
to assign high Ka sequences. Various models for fitting this spectrum are explored but, even without more extensive fits, we
are now able to present temperature scalable linelists for astrophysical applications.
a
b
J.Koput, J. Mol. Spectrosc. 115, 131 (1986).
Z.Kisiel et al., 65th OSU Symposium on Molecular Spectroscopy, The Ohio State University, Ohio 2010, RC-13.
104
TG09
4:03 – 4:18
GAS PHASE CONFORMATIONS AND METHYL INTERNAL ROTATION FOR 2-PHENYLETHYL METHYL ETHER
AND ITS ARGON VAN DER WAALS COMPLEX FROM FOURIER TRANSFORM MICROWAVE SPECTROSCOPY
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RANIL M. GURUSINGHE, MICHAEL TUBERGEN, Department of Chemistry and Biochemistry, Kent State
University, Kent, OH, USA.
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A mini-cavity microwave spectrometer was used to record the rotational spectra arising from 2-phenylethyl methyl ether
and its weakly bonded argon complex in the frequency range of 10.5 – 22 GHz. Rotational spectra were found for two stable
conformations of the monomer: anti-anti and gauche-anti, which are 1.4 kJ mol−1 apart in energy at wB97XD/6-311++G(d,p)
level. Doubled rotational transitions, arising from internal motion of the methyl group, were observed for both conformers.
The program XIAM was used to fit the rotational constants, centrifugal distortion constants, and barrier to internal rotation
to the measured transition frequencies of the A and E internal rotation states. The best global fit values of the rotational
constants for the anti-anti conformer are A= 3799.066(3) MHz, B= 577.95180(17) MHz, C= 544.7325(3) MHz and the A
state rotational constants of the gauche-anti conformer are A= 2676.1202(7) MHz, B= 760.77250(2) MHz, C= 684.78901(2)
MHz.
The rotational spectrum of 2-phenylethyl methyl ether – argon complex is consistent with the geometry where argon
atom lies above the plane of the benzene moiety of gauche-anti conformer. Tunneling splittings were too small to resolve
within experimental accuracy, likely due to an increase in three fold potential barrier when the argon complex is formed.
Fitted rotational constants are A= 1061.23373(16) MHz, B= 699.81754(7) MHz, C= 518.33553(7) MHz.
The lowest energy solvated ether - water complex with strong intermolecular hydrogen bonding has been identified
theoretically. Progress on the assignment of the water complex will also be presented.
TG10
4:20 – 4:30
A COMPARISON OF BARRIER TO METHYL INTERNAL ROTATION OF METHYLSTYRENES: MICROWAVE SPECTROSCOPIC STUDY
RANIL M. GURUSINGHE, MICHAEL TUBERGEN, Department of Chemistry and Biochemistry, Kent State
University, Kent, OH, USA.
Rotational spectra of α-Methylstyrene, cis-β-Methylstyrene, and trans-β-Methylstyrene were examined to investigate
their intrinsic tunneling properties. Theoretical calculations at wB97XD/6-311++G(d,p) level predict only one stable conformer for each molecular system. Spectra were recorded in the frequency range of 10.5 - 22.0 GHz using a cavity based
Fourier transform microwave spectrometer.
A relaxed potential scan for the methyl torsion at wB97XD/6-311++G(d,p) level of theory was used to estimate the
associated barrier for the hindered internal rotation. The program XIAM was used to fit the rotational constants, distortion
constants and barrier to methyl internal rotation to the measured transition frequencies of the A and E internal rotation states.
TG11
MICROWAVE SPECTRA AND AB INITIO STUDIES OF THE NE-ACETONE COMPLEX
4:32 – 4:47
JIAO GAO, JAVIX THOMAS, YUNJIE XU, WOLFGANG JÄGER, Department of Chemistry, University of
Alberta, Edmonton, AB, Canada.
Microwave spectra of the neon-acetone van der Waals complex were measured using a cavity-based molecular beam
Fourier-transform microwave spectrometer in the region from 5 to 18 GHz. Both 20 Ne and 22 Ne containing isotopologues
were studied and both c- and weaker a-type rotational transitions were observed. The transitions are split into multiplets
due to the internal rotation of two methyl groups in acetone. Electronic structure calculations were done at the MP2 level
of theory with the 6-311++g (2d, p) basis set for all atoms and the internal rotation barrier height of the methyl groups was
determined to be about 2.8 kJ/mol. The ab initio rotational constants were the basis for our spectroscopic searches, but the
multiplet structures and floppiness of the complex made the quantum number assignment very difficult. The assignment was
finally achieved with the aid of constructing closed frequency loops and predicting internal rotation splittings using the XIAM
code.a Analyses of the spectra yielded rotational and centrifugal distortion constants, as well as internal rotation parameters,
which were interpreted in terms of structure and internal dynamics of the complex.
a
H. Hartwig and H. Dreizler, Z. Naturforsch. A 51, 923 (1996).
105
TG12
4:49 – 5:04
THE EFFECTS OF INTERNAL ROTATION AND
14
N QUADRUPOLE COUPLING IN N-METHYLDIACETAMIDE
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RAPHAELA KANNENGIEßER, KONRAD EIBL, Institute for Physical Chemistry, RWTH Aachen University,
Aachen, Germany; HA VINH LAM NGUYEN, CNRS et Universités Paris Est et Paris Diderot, Laboratoire
Interuniversitaire des Systèmes Atmosphériques (LISA), Créteil, France; WOLFGANG STAHL, Institute for
Physical Chemistry, RWTH Aachen University, Aachen, Germany.
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Acetyl- and nitrogen containing substances play an important role in chemical, physical, and especially biological
systems. This applies in particular for acetamides, which are structurally related to peptide bonds. In this work, Nmethyldiacetamide, CH3 N(COCH3 )2 , was investigated by a combination of molecular beam Fourier transform microwave
spectroscopy and quantum chemical calculations.
In N-methyldiacetamide, at least three large amplitude motions are possible: (1) the internal rotation of the methyl group
attached to the nitrogen atom and (2, 3) the internal rotations of both acetyl methyl groups. This leads to a rather complicated
torsional fine structure of all rotational transitions with additional quadrupole hyperfine splittings caused by the 14 N nucleus.
Quantum chemical calculations were carried out at the MP2/6-311++G(d,p) level of theory to support the spectral assignment. Conformational analysis was performed by calculating a full potential energy surface depending on the orientation
of the two acetyl groups. This yielded three stable conformers with a maximum energy difference of 35.2 kJ/mol.
The spectrum of the lowest energy conformer was identified in the molecular beam. The quadrupole hyperfine structure
as well as the internal rotation of two methyl groups could be assigned. For the N-methyl group and for one of the two acetyl
methyl groups, barriers to internal rotation of 147 cm−1 and of 680 cm−1 , respectively, were determined. The barrier of the
last methyl group seems to be so high that no additional splittings could be resolved.
Using the XIAM program, a global fit with a standard deviation on the order of our experimental accuracy could be
achieved.
TG13
5:06 – 5:21
A NEW HYBRID PROGRAM FOR FITTING ROTATIONALLY RESOLVED SPECTRA OF METHYLAMINE-LIKE
MOLECULES: APPLICATION TO 2-METHYLMALONALDEHYDE
ISABELLE KLEINER, Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA), CNRS et Universités Paris Est et Paris Diderot, Créteil, France; JON T. HOUGEN, Sensor Science Division, National Institute
of Standards and Technology, Gaithersburg, MD, USA.
A new hybrid-model fitting program for methylamine-like molecules has been developed, based on an effective Hamiltonian in which the ammonia-like inversion motion is treated using a tunneling formalism, while the internal-rotation motion is
treated using an explicit kinetic energy operator and potential energy function. The Hamiltonian in the computer program is
set up as a 2x2 partitioned matrix, where each diagonal block consists of a traditional torsion-rotation Hamiltonian (as in the
earlier program BELGI), and the two off-diagonal blocks contain all tunneling terms. This hybrid formulation permits the use
of the permutation-inversion group G6 (isomorphic to C3v ) for terms in the two diagonal blocks, but requires G12 for terms
in the off-diagonal blocks. Our first application of the new program is to 2-methylmalonaldehyde. Microwave data for this
molecule were previously fit (essentially to experimental measurement error) using an all-tunneling Hamiltonian formalism
to treat both large-amplitude-motions a . For 2-methylmalonaldehyde, the hybrid program achieves a fit of nearly the same
quality as that obtained by the all-tunneling program, but fits with the hybrid program eliminate a large discrepancy between
internal rotation barriers in the OH and OD isotopologues of 2-methylmalonaldehyde that arose in fits with the all-tunneling
program. Other molecules for application of the hybrid program will be mentioned.
a
V.V. Ilyushin, E.A. Alekseev, Yung-Ching Chou, Yen-Chu Hsu, J. T. Hougen, F.J. Lovas, L. Picraux, J. Mol. Spectrosc. 251 (2008) 56-63
106
TG14
5:23 – 5:38
DETERMINATION OF TORSIONAL BARRIERS OF ITACONIC ACID AND N-ACETYLETHANOLAMINE USING
CHIRPED-PULSED FTMW SPECTROSCOPY
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JOSIAH R BAILEY, TIMOTHY J McMAHON, RYAN G BIRD, Chemistry, University of Pittsburgh Johnstown,
Johnstown, PA, USA; DAVID PRATT, Chemistry, University of Vermont, Burlington, VT, USA.
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The ground state rotational spectrum of itaconic acid (methylenesuccinic acid) and N-acetylethanolamine (AEA) have
been collected and analyzed over the frequency range of 7-17.5 GHz. Both molecules displayed an unexpected tunneling
splitting pattern caused by a V2 and V3 barriers, respectively. AEA’s methyl rotor is directly connected to a carbonyl and is
expected to have too high of a barrier to internal motion. Itaconic acid contains no methyl groups or any symmetry, yet a
torsional splitting was observed. The origin of this motion as well their barrier heights and lowest energy conformations will
be discussed.
107
TH. Radicals
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Chair: Bernadette M. Broderick, University of Georgia, Athens, GA, USA
TH01
AB INITIO SIMULATION OF THE PHOTOELECTRON SPECTRUM FOR METHOXY RADICAL
1:30 – 1:45
in
LAN CHENG, Department of Chemistry, The University of Texas, Austin, TX, USA; MARISSA L. WEICHMAN,
JONGJIN B. KIM, Department of Chemistry, The University of California, Berkeley, CA, USA; TAKATOSHI
ICHINO, Department of Chemistry, The University of Texas, Austin, TX, USA; DANIEL NEUMARK, Department of Chemistry, The University of California, Berkeley, CA, USA; JOHN F. STANTON, Department of Chemistry, The University of Texas, Austin, TX, USA.
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A theoretical simulation of the photoelectron spectrum for the ground state of methoxy radical is reported based on the
quasidiabatic model Hamiltonian originally proposed by Köppel, Domcke, and Cederbaum. The parameters in the model
Hamiltonian have been obtained from ab initio coupled-cluster calculations. The linear and quadratic force constants have
been calculated using equation-of-motion coupled-cluster ionization potential method with the singles, doubles, and triples
(EOMIP-CCSDT) truncation scheme together with atomic natural orbital basis sets of triple-zeta quality (ANO1). The cubic and quartic force constants have been obtained from EOMIP-CCSD calculations with ANO basis sets of double-zeta
quality (ANO0), and the spin-orbit coupling constant has been computed at the EOMIP-CCSD/pCVTZ level. The nuclear
Schroedinger equation has been solved using the Lanzcos algorithm to obtain vibronic energy levels as well as the corresponding intensities. The simulated spectrum compares favorably with the recent high-resolution slow electron velocity-map
imaging experiment for vibronic levels up to 2000 cm−1 .
TH02
1:47 – 2:02
JAHN-TELLER COUPLING IN THE METHOXY RADICAL: INSIGHTS INTO THE INFRARED SPECTRUM OF
MOLECULES WITH VIBRONIC COUPLING
BRITTA JOHNSON, EDWIN SIBERT, Department of Chemistry, The Univeristy of Wisconsin, Madison, WI,
USA.
The ground X̃ 2 E vibrations of the methoxy radical have intrigued both experimentalists and theorists alike due to
the presence of a conical intersection at the C3v molecular geometry. This conical intersection causes methoxy’s vibrational
spectrum to be strongly influenced by Jahn-Teller coupling which leads to large amplitude vibrations and extensive mixing
of the two lowest electronic states. The spectrum is further complicated due to spin-orbit and Fermi couplings. The standard
diabatic normal mode quantum numbers are poor labels due to this vibronic mixing.
Using the potential energy force field and calculated spectra of the methoxy radical by Nagesh and Sibert1 as a
starting point, we look to develop a method for assigning states to a spectrum with vibronic coupling. We simplify the analysis
by considering only the lowest two e modes of methoxy (the rock and the bend). When we include first-order Jahn-Teller
coupling between these two modes in a new zero-order Hamiltonian, we are able to use an expanded version of the linear
Jahn-Teller quantum numbers to assign the states.2 This zeroth order representation is nontrivial; therefore, we study the
properties of its eigenstates using correlation diagrams with respect to the strength of the Jahn-Teller coupling constant.
1
Nagesh, J.; Sibert, E. L. J. Phys. Chem. A 2012, 116, 3846–3855.
2
Barckholtz, T. A.; Miller, T. A. Int. Revs. in Phys. Chem. 1998, 17, 435–524.
108
TH03
RE-EVALUATION OF HO3 STRUCTURE USING MILLIMETER-SUBMILLIMETER SPECTROSCOPY
2:04 – 2:19
LUYAO ZOU, BRIAN HAYS, SUSANNA L. WIDICUS WEAVER, Department of Chemistry, Emory University, Atlanta, GA, USA.
in
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The HO3 radical is of great interest in both atmospheric and astrophysical chemistry. However, its molecular structure
has not been fully characterized by previous spectral studies. Microwave spectral studies on the trans-HO3 conformer did not
access higher Ka levels due to their limited frequency range. As a result, several centrifugal distortion constants could not be
determined. We have therefore conducted spectroscopy of HO3 in the millimeter and submillimeter ranges, from 70 to 450
GHz, under the guidance of a new fast sweep technique we developed for line searching. Large frequency shifts, primarily due
to a large ∆K centrifugal distortion constant, are observed compared to the spectral extrapolation from previous microwave
studies. In addition, new spectral branches have been detected. The measured lines and preliminary spectral analysis will be
presented, and the implications of these results will be discussed.
TH04
2:21 – 2:36
ON THE STARK EFFECT IN OPEN SHELL COMPLEXES EXHIBITING PARTIALLY QUENCHED ELECTRONIC
ANGULAR MOMENTUM
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GARY E. DOUBERLY, CHRISTOPHER P. MORADI, Department of Chemistry, University of Georgia, Athens,
GA, USA.
The Stark effect is considered for polyatomic open shell complexes that exhibit partially quenched electronic angular
momentum. Specifically, a zero-field model Hamiltonian is employed that accounts for the partial quenching of electronic
orbital angular momentum in hydroxyl radical containing molecular complexes.a,b Spherical tensor operator formalism is
employed to derive matrix elements of the Stark Hamiltonian in a parity conserving, Hund’s case (a) basis for the most
general case, in which the permanent dipole moment has projections on all three inertial axes of the system. Ro-vibrational
transition intensities are derived, again for the most general case; namely, the laser polarization is projected onto axes parallel
and perpendicular to the Stark electric field, and the transition dipole moment vector is projected onto all three inertial axes
in the molecular frame. The model discussed here is compared to experimental spectra of OH-(C2 H2 ), OH-(C2 H4 ), and
OH-(H2 O) complexes formed in He nanodroplets.
a
b
M. D. Marshall and M. I. Lester, J. Chem. Phys. 121, 3019 (2004).
G. E. Douberly, P. L. Raston, T. Liang, and M. D. Marshall, J. Chem. Phys. in press
TH05
2:38 – 2:53
INFRARED LASER SPECTROSCOPY AND AB INITIO COMPUTATIONS OF OH···(D2 O)N COMPLEXES IN HELIUM
NANODROPLETS
JOSEPH T. BRICE, CHRISTOPHER M. LEAVITT, CHRISTOPHER P. MORADI, GARY E. DOUBERLY, Department of Chemistry, University of Georgia, Athens, GA, USA; FEDERICO J HERNANDEZ, GUSTAVO A
PINO, INFIQC (CONICET – Universidad Nacional de Córdoba) Dpto. de Fisicoquı́mica – Facultad de Ciencias
Quı́, Universidad Nacional de Córdoba, Ciudad Universitaria, Córdoba, Argentina.
OH···(D2 O)N complexes are assembled in He droplets via the sequential pickup of D2 O molecules and the hydroxyl
radical, which is formed via the pyrolytic decomposition of tert-butyl hydroperoxide. Bands due to clusters as large as N=4
are observed. Ro-vibrational spectroscopy of the binary complex reveals a vibrationally averaged C2v structure. The effect of
partially quenched electronic angular momentum in the complex is partially resolved in the rotational fine structure associated
with the ν1 OH stretch. Stark spectroscopy of this band reveals a permanent electric dipole moment for the binary complex
equal to 3.70(5) Debye. OH stretch bands in larger clusters do not exhibit rotational fine structure; however, polarization
spectroscopy of the OH···(D2 O)2 complex, when compared to predictions from ab initio computations, reveals two nearly
isoenergetic isomers, both of which resemble the cyclic water trimer. Lower frequency OH stretch bands are assigned to
cyclic tetramer and cyclic pentamer clusters on the basis of D2 O pressure dependence and ab initio frequency computations.
109
TH06
2:55 – 3:10
VIBRATIONAL-TORSIONAL COUPLING REVEALED IN THE INFRARED SPECTRUM OF HE-SOLVATED nPROPYL RADICAL
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CHRISTOPHER P. MORADI, BERNADETTE M. BRODERICK, JAY AGARWAL, HENRY F. SCHAEFER
III., GARY E. DOUBERLY, Department of Chemistry, University of Georgia, Athens, GA, USA.
Pacansky, et. al., J. Phys. Chem. 1977, 81, 2149.
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The n-propyl and i-propyl radicals were generated in the gas phase via pyrolysis of n-butyl nitrite (CH3 (CH2 )3 ONO)
and i-butyl nitrite (CH3 CH(CH3 )CH2 ONO) precursors, respectively. Nascent radicals were promptly solvated by a beam of
He nanodroplets, and the infrared spectra of the radicals were recorded in the C-H stretching region. In addition to three
vibrations of n-propyl previously measured in an Ar matrix,a we observe many unreported bands between 2800 and 3150
cm−1 , which we attribute to propyl radicals. The C-H stretching modes observed above 2960 cm−1 for both radicals are
in excellent agreement with anharmonic frequencies computed using VPT2. Between 2800 and 2960 cm−1 , however, the
spectra of n-propyl and i-propyl radicals become quite congested and difficult to assign due to the presence of multiple
anharmonic resonances. Computations reveal the likely origin of the spectral congestion to be strong coupling between the
high frequency C-H stretching modes and a lower frequency torsional motion, which modulates quite substantially a throughspace hyperconjugation interaction.
TH07
3:12 – 3:27
VIBRONIC SPECTROSCOPY OF HETERO DIHALO-BENZYL RADICALS GENERATED BY CORONA DISCHARGE
: JET-COOLED CHLOROFLUOROBENZYL RADICALS
YOUNG YOON, SANG LEE, Department of Chemistry, Pusan National University, Pusan, Korea.
The technique of corona excited supersonic jet expansion coupled with a pinhole-type glass nozzle was applied to vibronic spectroscopy of jet-cooled chlorofluorobenzyl radicals for the vibronic assignments and measurements of electronic
energies of the D1 → D0 transition. The vibronic emission spectra were recorded with a long-path monochromator in the
visible region. The 2,3-, 2,4-,a and 2,5-b chlorofluorobenzyl radicals were generated by corona discharge of corresponding
precursor molecules, chlorofluorotoluenes seeded in a large amount of helium carrier gas. The emission spectra show the
vibronic bands originating from two benzyl-type radicals, chlorofluorobenzyl and fluorobenzyl benzyl radicals, in which fluorobenzyl radicals were obtained by displacement of Cl by H atom produced by the dissociation of methyl C-H bond. From
an analysis of the spectra observed, we could determine the electronic energies in D1 → D0 transition and vibrational mode
frequencies at the D0 state of chlorofluorobenzyl radicals which show the origin band of the electronic transition to be shifted
to red region, comparing with the parental benzyl radical. The red-shift is highly sensitive to the number, position, and kind
of substituents in chlorofluorobenzyl radicals. From the quantitative analysis of the red-shift, it has been found that the additivity rule, discovered recently by Lee group predicts the observation very well. In addition, the negligible contribution of
the substituent at the 4-position, the nodal point of the Hückel’s molecular orbital theory, can be well describes by the disconnection of substituent from molecular plane of the benzene ring available for delocalized π electrons. In this presentation, I
will discuss the spectroscopic observation of new chlorofluorobenzyl radicals and substituent effect on electronic transition
energy which is useful for identification of isomeric substituted benzyl radicals.
a
b
C. S. Huh, Y. W. Yoon, and S. K. Lee, J. Chem. Phys. 136, 174306 (2012).
S. Y. Chae, Y. W. Yoon, and S. K. Lee, Chem. Phys. Lett. 612, 134 (2014).
110
TH08
3:29 – 3:44
GROWING UP RADICAL: INVESTIGATION OF BENZYL-LIKE RADICALS WITH INCREASING CHAIN LENGTHS
JOSEPH A. KORN, KHADIJA M. JAWAD, DANIEL M. HEWETT, TIMOTHY S. ZWIER, Department of
Chemistry, Purdue University, West Lafayette, IN, USA.
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Combustion processes involve complex chemistry including pathways leading to polyaromatic hydrocarbons (PAHs)
from small molecule precursors. Resonance stabilized radicals (RSRs) likely play an important role in the pathways to PAHs
due to their unusual stability. Benzyl radical is a prototypical RSR that is stabilized by conjugation with the phenyl ring.
Earlier work on α-methyl benzyl radical showed perturbations to the spectroscopy due to a hindered methyl rotor.a If the
alkyl chain is lengthened then multiple conformations become possible. This talk will discuss the jet-cooled spectroscopy of
α-ethyl benzyl radical and α-propyl benzyl radical produced from the discharge of 1-phenyl propanol and 1-phenyl butanol
respectively. Electronic spectra were obtained via resonant two-photon ionization, and IR spectra were obtained by resonant
ion-dip infrared spectroscopy.
in
a
Kidwell, N. M.; Reilly, N. J.; Nebgen, B.; Mehta-Hurt, D. N.; Hoehn, R. D.; Kokkin, D. L.; McCarthy, M. C.; Slipchenko, L. V.; Zwier, T. S. The Journal of Physical Chemistry
A 2013, 117, 13465.
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Intermission
TH09
ANALYSIS OF ROTATIONALLY RESOLVED SPECTRA TO NON-DEGENERATE
LEVELS IN THE Ã2 E ′′ − X̃ 2 A′2 ELECTRONIC TRANSITION OF NO3
4:03 – 4:18
(a′′1 )
UPPER-STATE VIBRONIC
MOURAD ROUDJANE, TERRANCE JOSEPH CODD, Department of Chemistry and Biochemistry, The Ohio
State University, Columbus, OH, USA; MING-WEI CHEN, Department of Chemistry, University of Illinois at
Urbana-Champaign, Urbana, IL, USA; HENRY TRAN, DMITRY G. MELNIK, TERRY A. MILLER, Department of Chemistry and Biochemistry, The Ohio State University, Columbus, OH, USA; JOHN F. STANTON,
Department of Chemistry, The University of Texas, Austin, TX, USA.
The vibronic structure of the Ã − X̃ electronic spectrum of NO3 has been observed using both room-temperature and
jet-cooled samples. A recent analysis of this structure is consistent with the Jahn-Teller effect (JTE) in the e′ ν3 vibrational
mode (N-O stretch) being quite strong while the JTE in the e′ ν4 mode (O-N-O) bend) is rather weak. Electronic structure
calculations qualitatively predict these results but the calculated magnitude of the JTE is quantitatively inconsistent with the
spectral analysis.
Rotationally resolved spectra have been obtained for over a dozen vibronic bands of the Ã − X̃ electronic transition in
NO3 . An analysis of these spectra should provide considerably more experimental information about the JTE in the Ã state
of NO3 as the rotational structure should be quite sensitive to the geometric distortion of the molecule due to the JTE. This
talk will focus upon the parallel bands, which terminate on Ã state levels of a′′1 vibronic symmetry, which were the subject of
a preliminary analysis reported at this meeting in 2014. We have now recorded the rotational structure of over a half-dozen
parallel bands and have completed analysis on the 310 and 310 410 transitions with several other bands being reasonably well
understood. Two general conclusions emerge from this work. (i) All the spectral bands show evidence of perturbations which
can reasonably be assumed to result from interactions of the observed Ã state levels with high vibrational levels of the X̃ state.
The perturbations range from severe in some bands to quite modest in others. (ii) Analyses of observed spectra, insofar as
the perturbations permit, have all been performed with an oblate symmetric top model including only additional spin-rotation
effects. This result is, of course, consistent with an effective, undistorted geometry for NO3 of D3h symmetry on the rotational
timescale.
111
TH10
4:20 – 4:35
′
ANALYSIS OF ROTATIONALLY RESOLVED SPECTRA TO DEGENERATE (e ) UPPER-STATE VIBRONIC LEVELS
IN THE Ã2 E ′′ − X̃ 2 A′2 ELECTRONIC TRANSITION OF NO3
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HENRY TRAN, TERRY A. MILLER, Department of Chemistry and Biochemistry, The Ohio State University,
Columbus, OH, USA.
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The vibronic structure of the NO3 radical in the Ã state has been the subject of considerable research in our group and
others worldwide. Recently we have collected high resolution, rotationally resolved cavity-ringdown spectra of a number of
e2 E ′′ state. Parallel bands to non-degenerate levels of a′′ vibronic symmetry
the vibronic bands terminating on levels of the A
1
in the Ã state, can mostly be satisfactorily fit using an oblate symmetric top Hamiltonian including the effects of spin rotation.
The perpendicular bands, to levels of e′ symmetry, are not as satisfactorily described using this Hamiltonian. In particular, the
rotational structure of the e′ levels has more transitions than the oblate top model predicts. For this reason we have developed
a new rovibronic Hamiltonian capable of analyzing the vibronically degenerate levels. This Hamiltonian is based upon a D3h
configuration for NO3 corresponding to rotation of an oblate symmetric top. Terms corresponding to coriolis, spin-rotation,
spin-orbit, and Jahn-Teller distortions are then added. The simulations of the e′ bands using this model show generally better
agreement with the high resolution spectra. Our preliminary analysis indicates only modest effects on the rotational structure
due to Jahn-Teller distortion. Details of the analysis of the e′ bands, particularly 210 , will be presented.
TH11
ROVIBRONIC VARIATIONAL CALCULATIONS OF THE NITRATE RADICAL
4:37 – 4:52
BRYAN CHANGALA, JILA, National Institute of Standards and Technology and Univ. of Colorado Department
of Physics, University of Colorado, Boulder, CO, USA; JOSHUA H BARABAN, Department of Chemistry,
University of Colorado, Boulder, CO, USA; JOHN F. STANTON, Department of Chemistry, The University of
Texas, Austin, TX, USA.
In recent years, sophisticated diabatic Hamiltonians have been developed in order to understand the low-energy vibronic
level structure of the nitrate radical (NO3 ), which exhibits strong coupling between the X̃ and doubly degenerate B̃ states.
Previous studies have reproduced the observed vibronic level positions up to 2000 cm−1 above the zero-point level, yet the
rotational structure has remained uninvestigated with ab initio methods. In this talk, we present calculations of the N ≥ 0
rovibronic structure of low-lying vibronic states of NO3 , in which complicated rovibrational and Coriolis interactions have
been observed. Our results include calculations using both adiabatic and diabatic Hamiltonians, enabling a direct comparison
between the two. We discuss extensions of our treatment to include spin-orbit and spin-rotation effects.
112
TH12
4:54 – 5:09
VIBRONIC STRUCTURE OF THE X̃
2
A′2
STATE OF NO3
MASARU FUKUSHIMAa , Information Sciences, Hiroshima City University, Hiroshima, Japan.
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We have measured dispersed fluorescence ( DF ) spectra from the single vibronic levels ( SVL’s ) of the B̃ 2 E ′ state
of jet cooled 14 NO3 and 15 NO3 , and found a new vibronic band around the ν1 fundamentalb . This new band has two
characteristics; (1) inverse isotope shift, and (2) unexpectedly strong intensity, i.e. comparable with that of the ν1 fundamental.
We concluded on the basis of the isotope effect that the terminated ( lower ) vibrational level of the new vibronic band should
have vibrationally a′1 symmetry, and assigned to the third over-tone of the ν4 asymmetric (e′ ) mode, 3ν4 (a′1 ). We also
assigned a weaker band at about 160 cm−1 above the new band to one terminated to 3ν4 (a′2 ). The 3ν4 (a′1 ) and (a′2 ) levels
are ones with l = ±3. Hirota proposed new vibronic coupling mechanismc which suggests that degenerate vibrational modes
can induce electronic orbital angular momentum ( L ) even in non-degenerate electronic states. We interpret this as a sort
of break-down of the Born-Oppenheimer approximation, and think that ±l induces ∓Λ̄, where Λ̄ expresses the pseudo-L;
for the present system, one of the components of the third over-tone level, |Λ = 0; v4 = 3, l = +3i, can have contributions
of |Λ̄ = −1; v4 = 3, l = +2i and | − 2; 3, +1i. Under this interpretation, it is expected that there is sixth-order vibronic
3 3
3 3
Q+ ), between |0; 3, +3i and |0; 3, −3i. The sixth-order coupling is weaker than the Renner-Teller
Q− + q−
coupling, (q+
2 2
2 2
4 4
4 4
term ( the fourth-order term, (q+
Q− + q−
Q+ ) ), but stronger than the eighth-order term, (q+
Q− + q−
Q+ ). It is well known
in linear molecules that the former shows huge separation, comparable with vibrational frequency, among the vibronic levels
of Π electronic states, and the latter shows considerable splitting, ∼10 cm−1 , at ∆ electronic states. Consequently, the
∼160 cm−1 splitting at v4 = 3 is attributed to the sixth-order interaction. The relatively strong intensity for the band to 3ν4
(a′1 ) can be interpreted as a part of the huge 0-0 band intensity, because the 3ν4 (a′1 ) level, |0; 3, ±3i, can connect with the
vibrationless level, |0; 0, 0i. 3ν4 (a′1 ) has two-fold intensity because of the vibrational wavefunction, |0; 3, +3i + |0; 3, −3i,
while negligible intensity is expected for 3ν4 (a′2 ) with |0; 3, +3i − |0; 3, −3i due to the cancellation. To confirm these
interpretations, experiments on rotationally resolved spectra are underway.
a
Author thanks T. Ishiwata and E. Hirota for their valuable discussion and support.
M. Fukushima and T. Ishiwata, paper WJ03, ISMS2013, and paper MI17, ISMS2014.
c
E. Hirota, J.M ol.Spectrosc., in press.
b
TH13
HIGH-RESOLUTION LASER SPECTROSCOPY OF
B 2 E ′ STATE
14
5:11 – 5:26
NO3 RADICAL: VIBRATIONALLY EXCITED STATES OF THE
KOHEI TADA, Graduate School of Science, Kobe University, Kobe, Japan; SHUNJI KASAHARA, Molecular
Photoscience Research Center, Kobe University, Kobe, Japan; TAKASHI ISHIWATA, Information Sciences,
Hiroshima City University, Hiroshima, Japan; EIZI HIROTA, The Central Office, The Graduate University for
Advanced Studies, Hayama, Kanagawa, Japan.
High-resolution fluorescence excitation spectra of 14 NO3 radical were intermittently recorded in the region 15860 cm−1
to 16050 cm−1 corresponding to the transitions to the vibrationally excited states of the B 2 E ′ state. Well-separated rotational
lines were found to disappear as the vibrational energy increases. The 16050 cm−1 region is almost unstructured even in the
high-resolution measurement, and its rotational analysis is almost impossible. The rotational assignment of the 15870 cm−1
region is possible and it has been undertaken by the ground state combination differences and the Zeeman effect observation.
113
TH14
STRUCTURAL CHARACTERIZATION OF HYDROXYL RADICAL ADDUCTS IN AQUEOUS MEDIA
5:28 – 5:43
IRENEUSZ JANIK, G. N. R. TRIPATHI, Radiation Laboratory, University of Notre Dame, Notre Dame, IN,
USA.
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The oxidation by the hydroxyl (OH) radical is one of the most widely studied reactions because of its central role in
chemistry, biology, organic synthesis, and photocatalysis in aqueous environments, wastewater treatment, and numerous
other chemical processes. Although the redox potential of OH is very high, direct electron transfer (ET) is rarely observed.
If it happens, it mostly proceeds through the formation of elusive OH adduct intermediate which facilitates ET and formation
of hydroxide anion. Using time resolved resonance Raman technique we structurally characterized variety of OH adducts to
sulfur containing organic compounds, halide ions as well as some metal cations. The bond between oxygen of OH radical
and the atom of oxidized molecule differs depending on the nature of solute that OH radical reacts with. For most of sulfur
containing organics, as well as halide and pseudo-halide ions, our observation suggested that this bond has two-center threeelectron character. For several metal aqua ions studied, the nature of the bond depends on type of the cation being oxidized.
Discussion on spectral parameters of all studied hydroxyl radical adducts as well as the role solvent plays in their stabilization
will be presented.
114
TI. Dynamics/Kinetics/Ultrafast
Chair: Patrick Vaccaro, Yale University, New Haven, CT, USA
1:30 – 1:45
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TI01
MULTISCALE SPECTROSCOPY OF DIFFUSING MOLECULES IN CROWDED ENVIRONMENTS
AHMED A HEIKAL, Chemistry and Biochemistry, University of Minnesota Duluth, Duluth, MN, USA.
in
Living cells are known to be crowded with organelles, biomembranes, and macromolecules such as proteins, DNA,
RNA, and actin filaments. It is believed that such macromolecular crowding affect biomolecular diffusion, protein-protein
and protein-substrate interaction, and protein folding. In this contribution, I will discuss our recent results on rotational and
translational diffusion of small and large molecules in crowded environments using time-resolved anisotropy and fluorescence
correlation spectroscopy methods. In these studies, rhodamine green and enhanced green fluorescent protein are used as
fluorescent probes diffusing in buffers enriched with biomimetic crowding agents such as Ficoll-70, bovine serum albumin
(BSA), and ovalbumin. Controlled experiments on pure and glycerol-rich buffers were carried out as environments with
variable, homogeneous viscosity. Our results indicate that the microviscosity differs from the corresponding bulk viscosity,
depending on the nature of crowding agents (i.e., proteins versus polymers), the concentration of crowding agents and spatiotemporal scaling of our experimental approach. Our findings provide a foundation for fluorescence-based studies of diffusion
and binding of biomolecules in the crowded milieu of living cells.
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TI02
1:47 – 1:57
INVESTIGATING THE ROLE OF HUMAN SERUM ALBUMIN ON THE EXCITED STATE DYNAMICS OF INDOCYANINE GREEN USING SHAPED FEMTOSECOND LASER PULSESa
MUATH NAIRATb , ARKAPRABHA KONAR, MARIE KANIECKI, VADIM V. LOZOVOY, MARCOS DANTUSc , Department of Chemistry, Michigan State University, East Lansing, MI, USA.
Differences in the excited state dynamics of molecules and photo-activated drugs either in solution or confined inside
protein pockets or large biological macromolecules occur within the first few hundred femtoseconds. Shaped femtosecond
laser pulses are used to probe the behavior of indocyanine green (ICG), the only Food and Drug administration (FDA)
approved near-infrared dye and photodynamic therapy agent, while free in solution and while confined inside the pocket of
the human serum albumin (HSA) protein. Experimental findings indicate that the HSA pocket hinders torsional motion and
thus mitigates the triplet state formation in ICG. Low frequency vibrational motion of ICG is observed more clearly when it
is bound to the HSA protein.
a
b
c
Phys. Chem. Chem. Phys 17, 5872-5877 (2015)
[email protected]
[email protected]
TI03
1:59 – 2:14
ULTRAFAST SPECTROSCOPIC AND AB INITIO COMPUTATIONAL INVESTIGATIONS ON SOLVATION
DYNAMICS OF NEUTRAL AND DEPROTONATED TYROSINE.
TAKASHIGE FUJIWARA, Center for Photochemical Sciences, Bowling Green State University, Bowling Green,
OH, USA; MAREK Z. ZGIERSKI, Steacie Laboratory, National Research Council of Canada, Ottawa, ON,
Canada.
We have studied one of the aromatic amino acids, tyrosine, regarding its photophysical properties in various solvent
conditions by using a femtosecond fluorescence up-conversion technique and high-level TDDFT and CC2 computations. In
this talk, profound details not only on ultrafast solvation dynamics on a neutral tyrosine in various solvents, but also on the
excited-state dynamics for a single- (or doubly-) deprotonated tyrosine under various pH solutions will be presented. In
high basicity, a tyrosine shows different absorption/emission spectra, and a total spectrum consists of a combination of these
individual spectra that depend on the pH of the solution. The time scale of acid–base equilibrium is essential in solvation
dynamics; whereas the protonation is simply controlled by diffusion, the de-protonation is considered to be slow process
such that acid–base equilibrium may not be reached in the short-lived excited state after photo-excitation. Experimental and
computational approaches taken and insights obtained in this concerted work will be described.
115
TI04
2:16 – 2:31
WHICH ELECTRONIC AND STRUCTURAL FACTORS CONTROL THE PHOTOSTABILITY OF DNA AND RNA
PURINE NUCLEOBASES?
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MARVIN POLLUM, CHRISTIAN REICHARDT, CARLOS E. CRESPO-HERNÁNDEZ, Chemistry, Case
Western Reserve, Cleveland, OH, USA; LARA MARTÍNEZ-FERNÁNDEZ, INÉS CORRAL, Departamento de
Quimica, Universidad Autonoma de Madrid, Madrid, Spain; CLEMENS RAUER, SEBASTIAN MAI, PHILIPP
MARQUETAND, LETICIA GONZÁLEZ, Institute for Theoretical Chemistry, University of Vienna, Vienna,
Austria.
in
Following ultraviolet excitation, the canonical purine nucleobases, guanine and adenine, are able to efficiently dissipate
the absorbed energy within hundreds of femtoseconds. This property affords these nucleobases with great photostability.
Conversely, non-canonical purine nucleobases exhibit high fluorescence quantum yields or efficiently populate long-lived
triplet excited states from which chemistry can occur. Using femtosecond broadband transient absorption spectroscopy in
combination with ab initio static and surface hopping dynamics simulations we have determined the electronic and structural
factors that regulate the excited state dynamics of the purine nucleobase derivatives. Importantly, we have uncovered that the
photostability of the guanine and adenine nucleobases is not due to the structure of the purine core itself and that the substituent
at the C6 position of the purine nucleobase plays a more important role than that at the C2 position in the ultrafast relaxation
of deleterious electronic energy. [The authors acknowledge the CAREER program of the National Science Foundation (Grant
No. CHE-1255084) for financial support.]
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TI05
2:33 – 2:48
ULTRAFAST DYNAMICS IN DNA AND RNA DERIVATIVES MONITORED BY BROADBAND TRANSIENT ABSORPTION SPECTRSCOPY
MATTHEW M BRISTER, Department of Chemistry, Case Western Reserve University, Cleveland, OH, USA;
CARLOS E. CRESPO-HERNÁNDEZ, Chemistry, Case Western Reserve, Cleveland, OH, USA.
The ultrafast dynamics of nucleic acids have been under scrutiny for the past couple of decades because of the role that
the high-energy electronic states play in mutagenesis and carcinogenesis. Kinetic models have been proposed, based on both
experimental and theoretical discoveries. Direct experimental evidence of the intersystem crossing rate and population of the
triplet state for most nucleic acid bases has yet to be reported, even though the triplet state is thought to be the most reactive
species. Utilizing broadband femtosecond transient absorption spectroscopy, we reveal the time scale at which singlet-totriplet population transfer occurs in several nucleic acid derivatives in the condensed phase. The implication of these results
to the current understanding of the DNA and RNA photochemistry will be discussed. The authors acknowledge the CAREER
program of the National Science Foundation (Grant No. CHE-1255084) for financial support.
TI06
2:50 – 3:05
CAN FEMTOSECOND TRANSIENT ABSORPTION SPECTROSCOPY PREDICT THE POTENTIAL OF SMALL
MOLECULES AS PERSPECTIVE DONORS FOR ORGANIC PHOTOVOLTAICS?
REGINA DISCIPIO, GENEVIEVE SAUVE, Department of Chemistry, Case Western Reserve University, Cleveland, OH, USA; CARLOS E. CRESPO-HERNÁNDEZ, Chemistry, Case Western Reserve, Cleveland, OH, USA.
The utility of a perspective donor or acceptor molecule for photoelectric applications is difficult to predict a priori. This
hinders productive synthetic exploration and necessitates lengthy device optimization procedures for reasonable estimation of
said molecule’s applicability. Using femtosecond broadband transient absorption spectroscopy, supported by time-dependent
density functional theory computations and steady-state-absorption and emission spectroscopies, we have characterized a
family of perspective optoelectronic compounds, in an effort to predict their relative performance in organic photovoltaic
devices from information accrued from excited-state dynamics and photophysical properties.
A series of tetraphenylazadipyrromethene (ADP) complexes chelated with three different metal centers was investigated.
We have determined that the chelating metal has little effect on the ground state properties of this family. However their
excited state dynamics are strongly modulated by the metal. Specifically, the zinc-chelated ADP complex remains in the
excited state tenfold longer than the cobalt or nickel complexes. We assert that this is key photophysical property that should
make the zinc complex outperform the other two complexes in photovoltaic applications. This hypothesis is supported by
preliminary power conversion efficiency results in devices.
116
TI07
3:07 – 3:22
MOLECULE-LIKE CdSe NANOCLUSTERS PASSIVATED WITH STRONGLY INTERACTING LIGANDS: ENERGY
LEVEL ALIGNMENT AND PHOTOINDUCED ULTRAFAST CHARGE TRANSFER PROCESSES
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YIZHOU XIE, Department of Chemistry, University of Louisville, Louisville, KY, USA; MEGHAN B TEUNIS, Department of Chemistry, Indiana University-Purdue University Indianapolis, Indianapolis, IN, USA; BILL
PANDITa , Department of Chemistry, University of Louisville, Louisville, KY, USA; RAJESH SARDAR, Department of Chemistry, Indiana University-Purdue University Indianapolis, Indianapolis, IN, USA; JINJUN LIU,
Department of Chemistry, University of Louisville, Louisville, KY, USA.
Current address: Department of Chemistry, Northwestern University
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Semiconductor nanoclusters (SCNCs) are promising electronic materials for use in solid-state device fabrication, where
device efficiency is strongly controlled by charge generation and transfer from SCNCs to their surroundings. In this paper we
report the excited-state dynamics of molecule-like 1.6 nm diameter CdSe SCNCs, which are passivated with the highly conjugated ligand phenyldithiocarbamate (PDTC) or para-substituted PDTCs. Femtosecond transient absorption studies reveal
sub-picosecond hole transfer (τ ≈ 0.9 ps) from a SCNC to its ligand shell based on strong electronic interaction and hole
delocalization, and hot electron transfer (τ ≈ 0.2 ps) to interfacial states created by charge separation. A series of control
experiments were performed by varying SCNC size (1.6 nm v.s. 2.9 nm) and photon energy of the pump laser (388 nm v.s.
490 nm), as well as addition of electron quencher (benzoquinone) and hole quencher (pyridine), which rules out alternative
mechanisms and confirms the critical role of energy level alignment between the SCNC and its passivating ligands.
TI08
TOWARD THE ACCURATE SIMULATION OF TWO-DIMENSIONAL ELECTRONIC SPECTRA
3:24 – 3:39
ANGELO GIUSSANI, ARTUR NENOV, JAVIER SEGARRA-MARTÍ, VISHAL K. JAISWAL, Dipartimento di
Chimica G. Ciamician, Università di Bologna, Bologna, Italy; IVAN RIVALTA, ELISE DUMONT, Laboratoire
de Chimie, Ecole Normale Suprieure de Lyon, Lyon, FR; SHAUL MUKAMEL, Department of Chemistry, University of California, Irvine, Irvine, CA, USA; MARCO GARAVELLI, Dipartimento di Chimica G. Ciamician,
Università di Bologna, Bologna, Italy.
Two-dimensional pump-probe electronic spectroscopy is a powerful technique able to provide both high spectral and
temporal resolution, allowing the analysis of ultrafast complex reactions occurring via complementary pathways by the
identification of decay-specific fingerprints. [1-2] The understanding of the origin of the experimentally recorded signals in a two-dimensional electronic spectrum requires the characterization of the electronic states involved in the electronic transitions photoinduced by the pump/probe pulses in the experiment. Such a goal constitutes a considerable computational challenge, since up to 100 states need to be described, for which state-of-the-art methods as RASSCF and
RASPT2 have to be wisely employed. [3] With the present contribution, the main features and potentialities of twodimensional electronic spectroscopy are presented, together with the machinery in continuous development in our groups
in order to compute two-dimensional electronic spectra. The results obtained using different level of theory and simulations
are shown, bringing as examples the computed two-dimensional electronic spectra for some specific cases studied. [2-4]
[1] Rivalta I, Nenov A, Cerullo G, Mukamel S, Garavelli M, Int. J. Quantum
Chem., 2014, 114, 85 [2] Nenov A, Segarra-Martı́ J, Giussani A, Conti I, Rivalta I,
Dumont E, Jaiswal V K, Altavilla S, Mukamel S, Garavelli M, Faraday Discuss. 2015,
DOI: 10.1039/C4FD00175C [3] Nenov A, Giussani A, Segarra-Martı́ J, Jaiswal V K,
Rivalta I, Cerullo G, Mukamel S, Garavelli M, J. Chem. Phys. submitted [4] Nenov
A, Giussani A, Fingerhut B P, Rivalta I, Dumont E, Mukamel S, Garavelli M, Phys.
Chem. Chem. Phys. Submitted [5] Krebs N, Pugliesi I, Riedle E, New J. Phys.,
2013,15, 085016
Intermission
117
TI09
ULTRAFAST TERAHERTZ KERR EFFECT SPECTROSCOPY OF LIQUIDS AND BINARY MIXTURES
3:58 – 4:13
MARCO A. ALLODI, IAN A FINNERAN, GEOFFREY BLAKE, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA.
in
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The ultrafast TeraHertz Kerr effect (TKE) has recently been demonstrated as a nonlinear spectroscopic technique capable
of measuring the dielectric relaxation of liquids. The true power of this technique lies in its ability to provide complementary
information to measurements taken using heterodyne-detected optical Kerr effect (OKE) spectroscopy. The optical pulses in
OKE measurements interact with the sample via the molecular polarizability, a rank-two tensor, in contrast with THz pulses
that interact with the molecules via the dipole moment, a rank-one tensor. Given the different light-matter interactions in the
two techniques, TKE measurements help complete the physical picture of intermolecular interactions at short timescales.
We report here our implementation of heterodyne-detected TKE spectroscopy, along with measurements of pure liquids,
and binary mixtures. Some of the liquids presented here were previously believed to be TKE inactive, thus showing that we
have achieved a greater sensitivity than the previous implementation in the literature. In addition, we will discuss a variety
of binary mixtures and show how the TKE data can be compared with OKE data to deepen our physical understanding of
intermolecular interactions in liquids.
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TI10
ULTRAFAST TERAHERTZ KERR EFFECT SPECTROSCOPY OF AROMATIC LIQUIDS
4:15 – 4:30
IAN A FINNERAN, MARCO A. ALLODI, GEOFFREY BLAKE, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA.
Ultrafast Terahertz Kerr Effect (TKE) spectroscopy is a relatively new nonlinear THz technique that is sensitive to the
orientational dynamics of anisotropic, condensed-phase samples. The sample is excited by a single high field strength ∼1
picosecond THz pulse, and the resulting transient birefringence is measured by a ∼40 femtosecond 800 nm probe pulse. We
have measured the TKE response of several aromatic liquids at room temperature, including benzene, benzene-d6, hexafluorobenzene, pyridine, and toluene. The measured decay constants range from ∼1-10 ps, and, along with previous optical Kerr
effect results in the literaturea , give insights into intermolecular interactions in these liquids.
a
Loughnane et al. JPCB 110.11 (2006): 5708-5720.
TI11
4:32 – 4:47
VIBRATIONALLY-RESOLVED KINETIC ISOTOPE EFFECTS IN THE PROTON-TRANSFER DYNAMICS OF
GROUND-STATE TROPOLONE
KATHRYN CHEW, ZACHARY VEALEY, PATRICK VACCARO, Department of Chemistry, Yale University,
New Haven, CT, USA.
The vibrational and isotopic dependence of the hindered (tunneling-mediated) proton-transfer reaction taking place in the
ground electronic state (X̃1 A1 ) of monodeuterated tropolone (TrOD) has been explored under ambient (bulk-gas) conditions
by applying two-color variants of resonant four-wave mixing (RFWM) spectroscopy in conjunction with polarization-resolved
detection schemes designed to alleviate spectral complexity and facilitate rovibrational assignments. Full rotation-tunneling
analyses of high-resolution spectral profiles acquired for the fundamental and first-overtone bands of a reaction-promoting
O−D· · · O deformation/ring-breathing mode, ν36 (a1 ), were performed, thereby extracting refined structural and dynamical
information that affords benchmarks for the quantitative interpretation of tunneling-induced signatures found in long-range
−1
scans of X̃1 A1 vibrational levels residing below E X̃
. Observed kinetic isotope effects, which reflect changes
vib = 1700 cm
in both reaction kinematics and vibrational displacements, will be discussed, with high-level quantum-chemical calculations
serving to elucidate state-resolved propensities for proton transfer in TrOH and TrOD.
118
TI12
CHARACTERIZATION OF CHBrCl2 PHOTOLYSIS BY VELOCITY MAP IMAGING
4:49 – 5:04
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W G MERRILL, AMANDA CASE, Department of Chemistry, The Univeristy of Wisconsin, Madison, WI, USA;
BENJAMIN C. HAENNI, Department of Chemistry, University of Wisconsin–Madison, Madison, WI, USA;
ROBERT J. McMAHON, FLEMING CRIM, Department of Chemistry, The Univeristy of Wisconsin, Madison,
WI, USA.
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Halomethanes have attracted extensive research efforts of considerable variety, owing to their relative simplicity and
ubiquitous presence in synthetic and environmental settings as well as their amenability to benchmark problems in physical
chemistry. Their role in atmospheric processes is well known, most famously as the source of atomic halogens which catalyze
the depletion of stratospheric ozone. Indeed, the photolytic cleavage of the carbon-halogen bond is the primary fate of
halomethanes in the atmosphere. We utilize laser-induced photolysis to study the C-Br bond cleavage in CHBrCl2 in a
molecular beam. Atomic bromine fragments are probed with resonance enhanced multiphoton ionization (REMPI), which
allows ground state and spin-excited products to be independently detected. Action spectroscopy in conjunction with velocity
map imaging is used to determine the internal energy of the CHCl2 partner fragment. Product state distributions as a function
of photolysis energy may be discerned with these techniques. Current results will be presented.
TI13
1
5:06 – 5:21
1
REVERSIBILITY OF INTERSYSTEM CROSSING IN THE ã A1 (000) and ã A1 (010) STATES OF METHYLENE, CH2
ANH T. LE, TREVOR SEARSa , GREGORY HALL, Chemistry Department, Brookhaven National Laboratory,
Upton, NY, USA.
The lowest energy singlet (ã1 A1 ) and triplet (X̃ 3 B1 ) electronic states of methylene, CH2 , are only separated by 3150
cm , but differ greatly in chemical reactivity. Overall methylene reaction rates and chemical behavior are therefore strongly
dependent on collisionally-mediated singlet-triplet interconversion. Collisions with inert partners tend to depopulate the excited singlet state and populate vibrationally excited triplet levels in CH2 . This process is generally considered as irreversible
for large molecules, however, this is not the case for small molecules such as CH2 . An investigation of the decay kinetics
of CH2 in the presence of argon and various amounts of oxygen has been carried out using transient frequency modulation
(FM) absorption spectroscopy, to monitor ortho and para rotational levels in both the ã1 A1 (000) and ã1 A1 (010) states. In the
ã1 A1 (000) state, all observed rotational levels follow double exponential decay kinetics, a direct consequence of reversible intersystem crossing. The relative amplitude of the slower decay component is an indicator of how quickly the reverse crossing
from excited triplet levels becomes significant during the reaction and relaxation of singlet methylene. The para rotational
levels show more obvious signs of reversibility than ortho rotational levels. Adding oxygen enhances the visibility of reversibility for both ortho and para levels. However, in the ã1 A1 (010) state where the FM signal is 5-10 times smaller than
the ã1 A1 (000) state, there is no evidence of double exponential decay kinetics.
Acknowledgments: Work at Brookhaven National Laboratory was carried out under Contract No. DE-AC02-98CH10886
and DE-SC0012704 with the U.S. Department of Energy and supported by its Office of Basic Energy Sciences, Division of
Chemical Sciences, Geosciences and Biosciences.
−1
a
Also, Chemistry Department, Stony Brook University, Stony Brook, New York 11794
119
TI14
5:23 – 5:38
EFFICIENT SUPER ENERGY TRANSFER COLLISIONS THROUGH REACTIVE-COMPLEX FORMATION: H + SO2
ar
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JONATHAN M. SMITH, MICHAEL J. WILHELM, Department of Chemistry, Temple University, Philadelphia,
PA, USA; JIANQIANG MA, Chemistry, Columbia University, New York, New York, USA; HAI-LUNG DAI,
Department of Chemistry, Temple University, Philadelphia, PA, USA.
in
Translational-to-vibrational energy transfer (ET) from a hyperthermal H atom to ambient SO2 was characterized using
time-resolved Fourier transform infrared emission spectroscopy. Vibrational excitation of SO2 , following collisions with H
atoms containing 59 kcal/mol of kinetic energy, generated from the 193 nm photolysis of HBr, is detected in two distinct
energy distributions: one with excitation predominantly at the fundamental vibrational levels is attributable to classical impulsive collisions, while the other, accounting for 80% of the excited SO2 with vibrational energy as high as 14,000 cm−1 ,
is proposed to arise from the formation of a transient reactive-complex during the collision. The cross-section for this super
ET collision is determined to be 0.53±0.05 Å2 , or roughly 2% of all hard sphere collisions. This observation reveals that in
collisions between a hyperthermal atom and an ambient molecule, for which a reactive-complex exists on the potential energy
surface, a large quantity of translational energy can be transferred to the molecule with high efficiency.
TI15
FOURTH-ORDER VIBRATIONAL TRANSITION STATE THEORY AND CHEMICAL KINETICS
5:40 – 5:55
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JOHN F. STANTON, Department of Chemistry, The University of Texas, Austin, TX, USA; DEVIN A.
MATTHEWS, JUSTIN Z GONG, Department of Chemistry and Biochemistry, The University of Texas, Austin,
TX, USA.
Second-order vibrational perturbation theory (VPT2) is an enormously successful and well-established theory for treating
anharmonic effects on the vibrational levels of semi-rigid molecules. Partially as a consequence of the fact that the theory
is exact for the Morse potential (which provides an appropriate qualitative model for stretching anharmonicity), VPT2 calculations for such systems with appropriate ab initio potential functions tend to give fundamental and overtone levels that
fall within a handful of wavenumbers of experimentally measured positions. As a consequence, the next non-vanishing level
of perturbation theory – VPT4 – offers only slight improvements over VPT2 and is not practical for most calculations since
it requires information about force constants up through sextic. However, VPT4 (as well as VPT2) can be used for other
applications such as the next vibrational correction to rotational constants (the “gammas”) and other spectroscopic parameters. In addition, the marriage of VPT with the semi-classical transition state theory of Miller (SCTST) has recently proven
to be a powerful and accurate treatment for chemical kinetics. In this talk, VPT4-based SCTST tunneling probabilities and
cumulative reaction probabilities are give for the first time for selected low-dimensional model systems. The prospects for
VPT4, both practical and intrinsic, will also be discussed.
120
TJ. Rydberg Atoms and Molecules
ar
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Chair: Brian DeMarco, University of Illinois, Urbana, IL, USA
TJ01
1:30 – 1:45
PRECISION SPECTROSCOPY IN COLD MOLECULES: THE FIRST ROTATIONAL INTERVALS OF
RESOLUTION SPECTROSCOPY AND RYDBERG-SERIES EXTRAPOLATION
He+
2
BY HIGH-
in
PAUL JANSEN, LUCA SEMERIA, SIMON SCHEIDEGGER, FREDERIC MERKT, Laboratorium für
Physikalische Chemie, ETH Zurich, Zurich, Switzerland.
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Having only three electrons, He+
2 represents a system for which highly accurate ab initio calculations are possible. The
latest calculation of rovibrational energies in He+
2 do not include relativistic or QED corrections but claim an accuracy of about
120 MHza . The available experimental data on He+
2 , though accurate to 300 MHz, are not precise enough to rigorously test
these calculations or reveal the magnitude of the relativistic and QED corrections. We have performed high-resolution Rydberg spectroscopy of metastable He2 molecules and employed multichannel-quantum-defect-theory extrapolation techniquesb
to determine the rotational energy-level structure in the He+
2 ion. To this end we have produced samples of helium molecules
in the a3 Σ+
u state in supersonic beams with velocities tunable down to 100 m/s by combining a cryogenic supersonic-beam
source with a multistage Zeeman deceleratorc . The metastable He2 molecules are excited to np Rydberg states using the frequency doubled output of a pulse-amplified ring dye laser. Although the bandwidth of the laser systems is too large to observe
the reduction of the Doppler width resulting from deceleration, the deceleration greatly simplifies the spectral assignments
because of its spin-rotational state selectivity. Our approach enabled us to determine the rotational structure of He+
2 with
unprecedented accuracy, to determine the size of the relativistic and QED corrections by comparison with the results of Ref. a
and to precisely measure the rotational structure of the metastable state for comparison with the results of Focsa et al.d .
a
W.-C. Tung, M. Pavanello, L. Adamowicz, J. Chem. Phys. 136, 104309 (2012).
D. Sprecher, J. Liu, T. Krähenmann, M. Schäfer, and F. Merkt, J. Chem. Phys. 140, 064304 (2014).
c
M. Motsch, P. Jansen, J. A. Agner, H. Schmutz, and F. Merkt, Phys. Rev. A 89, 043420 (2014).
d
C. Focsa, P. F. Bernath, and R. Colin, J. Mol. Spectrosc. 191, 209 (1998).
b
TJ02
1:47 – 2:02
MICROWAVE SPECTROSCOPY OF THE CALCIUM 4snf → 4s(n + 1)d, 4sng, 4snh, 4sni, AND 4snk TRANSITIONS
JIRAKAN NUNKAEW, TOM GALLAGHER, Department of Physics, The University of Virginia, Charlottesville, VA, USA.
We use a delayed field ionization technique to observe the microwave transitions of calcium Rydberg states, from the
4snf states to the 4s(n + 1)d, 4sng, 4snh, 4sni, and 4snk states for 18 ≤ n ≤ 23. We analyze the observed intervals
between the ℓ and (ℓ + 1), ℓ ≥ 5, states of the same n to determine the Ca+ 4s dipole and quadrupole polarizabilities. We
show that the adiabatic core polarization model is not adequate to extract the Ca+ 4s dipole and quadrupole polarizabilities
and a non adiabatic treatment is required. We use the non adiabatic core polarization model to determine the ionic dipole and
quadrupole polarizabilities to be αd = 76.9(3) a30 and αq = 206(9) a50 , respectively.
121
TJ03
2:04 – 2:14
PHASE DEPENDENCE IN ABOVE THRESHOLD IONIZATION IN THE PRESENCE OF A MICROWAVE FIELD
VINCENT CARRAT, ERIC MAGNUSON, TOM GALLAGHER, Department of Physics, The University of
Virginia, Charlottesville, VA, USA.
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Energy (au)
ar
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Exciting an atom with high-frequency radiation in the presence
of a low frequency field can result in energy transfer between the
photoelectron and the low frequency field, depending on the phase
2 1e−5
of the low frequency field when the excitation occurs. We excite
1
Li atoms with IR lasers in the presence of a microwave field. In
p0⃗ p0⃗
a previous experiment, detection of highly excited states with ex0
citation by a ps laser tuned above the limit clearly showed a phase
dependence.
The variation of the signal due to a phase change reach
−1
0.1% of the total excitation in that case. We are using a new excitation scheme with a CW amplitude modulated laser, the modulation
−2
being phase locked to the microwaves. We now observe a signal
−3
variation of 10% of the total excitation. The ps pulses spreads the
A tom ic potential
population over a broad energy spectrum while the modulated exci−4
tation keeps it in narrow bands. The modulated laser frequency can
−1.0
−0.5
0.0
0.5
1.0
1e5
Radius (au)
be tuned to couple one band to the highly excited states, enhancing the collection efficiency, additionally it is closer to the limit.
Figure 1: Electrons gaining or losing energy during the Furthermore, the modulated laser allows the observation of phase
first microwave cycle depending of the initial launch- dependent transfer to both higher and lower energies. The observaing direction. Here the phase of the microwave field tions can be described with relatively simple models.
is adjusted to provide a maximum energy transfer. The
oscillations in energy are synchronized with the 14GHz
microwave field.
TJ04
MICROWAVE TRANSITIONS BETWEEN PAIR STATES COMPOSED OF TWO Rb RYDBERG ATOMS
2:16 – 2:26
JEONGHUN LEE, TOM GALLAGHER, Department of Physics, The University of Virginia, Charlottesville, VA,
USA.
Microwave transitions between pair states composed of two Rb Rydberg atoms in a magneto-optical trap are investigated.
Our current interest is the transition from ndnd to (n+1)d(n-2)f states. This transition is allowed because the dipole-dipole
induced configuration interaction between the ndnd state and the energetically close (n+2)p(n-2)f state admixes some of
the latter state into the former. The resonance frequencies of the ndnd-(n+1)d(n-2)f transitions for n=35 to 42 have been
measured and found to agree well with the calculated values. In addition, the power shifts of the resonance frequencies have
been measured for n=35 to 42. The dependence of the fractional population transfer from the ndnd to (n+1)d(n-2)f states on
the microwave field strength and atomic density has been measured and can be compared to a simple theoretical model. This
work has been supported by the Air Force Office of Scientific Research.
122
TJ05
2:28 – 2:43
HIGH-RESOLUTION SPECTROSCOPY OF LONG-RANGE MOLECULAR STATES OF
85
Rb2
RYAN CAROLLO, EDWARD E. EYLER, YOANN BRUNEAU, PHILLIP GOULD, W.C. STWALLEY, Department of Physics, University of Connecticut, Storrs, CT, USA.
in
ar
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We present analysis of low-n long-range molecular Rydberg states in 85 Rb2 , based on high-resolution spectra. The
weakly bound states are accessed by bound-bound transitions from high-v levels of the a 3 Σ+
u state, which are prepared by
photoassociation of laser-cooled atoms. Single-photon transitions to target states near the 5s + 7p asymptote are excited
by a frequency-doubled pulse-amplified CW laser with a narrow linewidth, under 200 MHz. The long-range portion of the
bonding potential is dominated by the elastic scattering interaction of the Rydberg electron of a perturbed 7p atom and a
nearby ground-state atom, in much the same manner as trilobite states. We use time of flight to selectively measure molecular
ions, which are formed via autoionization. This technique gives a two orders-of-magnitude improvement in linewidth over
our previous work, reported in Ref. [1]. We also present calculations of a proposed scheme for STIRAP transfer from
′′
the current v ′′ = 35 level of the a 3 Σ+
u state to the v = 39 level. The long-range states accessible to us are defined in
large part by the Franck-Condon factors, which are dominated by the outer lobe of the wavefunction. Thus, choosing a
v ′′ sets R, and determines the Franck-Condon window. The proposed v ′′ = 39 level has a classical outer turning point
at ∼ 72 a0 , and will provide access to higher-n states with longer-range wells. This work is supported by the NSF and AFOSR.
[1] M. A. Bellos et al., Phys. Rev. Lett. 111, 053001 (2013)
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TJ06
DOUBLE RESONANCE SPECTROSCOPY OF BaF AUTOIONIZING RYDBERG STATES
2:45 – 3:00
TIMOTHY J BARNUM, DAVID GRIMES, Department of Chemistry, MIT, Cambridge, MA, USA; YAN ZHOU,
JILA, National Institute of Standards and Technology and Univ. of Colorado Department of Physics, University
of Colorado, Boulder, Boulder, CO, USA; ROBERT W FIELD, Department of Chemistry, MIT, Cambridge, MA,
USA.
We have studied the ν=1 Rydberg states of BaF in the energy region E=38800-39100 cm−1 (n*=15-25) via opticaloptical double resonance spectroscopy. Rydberg states excited above the first ionization potential spontaneously autoionize
and 138 Ba19 F+ ions are detected by TOF-MS. In addition, BaF possesses a particularly low ionization potential, which
allows for the study of autoionization dynamics in the absence of predissociative decay. This work extends the assignments of
core-penetrating Rydberg states of BaF (Jakubek and Field, 2000) for applications to state-selective ion production schemes.
Polarization and Stark spectroscopy techniques will be discussed in the context of accurate and efficient assignment of spectra.
TJ07
3:02 – 3:17
MILLIMETER WAVE SPECTROSCOPY OF RYDBERG STATES OF MOLECULES IN THE REGION OF 260-295 GHz
DAVID GRIMES, Department of Chemistry, MIT, Cambridge, MA, USA; YAN ZHOU, JILA, National Institute
of Standards and Technology and Univ. of Colorado Department of Physics, University of Colorado, Boulder,
Boulder, CO, USA; TIMOTHY J BARNUM, ROBERT W FIELD, Department of Chemistry, MIT, Cambridge,
MA, USA.
Free induction decay detected chirped pulse millimeter wave spectroscopy of Rydberg-Rydberg transitions in atoms and
molecules is a powerful and flexible method for characterizing the electronic structure of Rydberg states and determining the
structure and dynamics of the ion-core. Complicating the use of this technique are the difficulties in reliably and repeatedly
accessing not just the most information rich core-nonpenetrating states, but also the low-ℓ core-penetrating Rydberg states
in the area of principal quantum number n∗ > 35. Small transition moments and narrow linewidths for transitions between
valence electronic states and high Rydberg states are the primary limiting factor. We demonstrate a simple method to avoid
the problem entirely by using chirped pulse technology operating in the frequency range of 260-295 GHz, which allows us
to sample a lower range of n∗ values than before with comparable frequency resolution and accuracy as our previous W-band
experiments. Further improvements to our experiment in order to accurately capture details of Stark demolition, a technique
that provides rapid differentiation between core-penetrating and core-nonpenetrating states, will also be discussed.
Intermission
123
TJ08
3:36 – 3:51
EFFECTIVE ION-IN-MOLECULE POTENTIALS FOR NON-PENETRATING RYDBERG STATES OF POLAR
MOLECULES
ar
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STEPHEN COY, DAVID GRIMES, YAN ZHOU, ROBERT W FIELD, Department of Chemistry, MIT, Cambridge, MA, USA; BRYAN M. WONG, Department of Chemistry, University of California, Riverside, Riverside,
Ca, USA.
TJ09
1
in
Rydberg states of atoms or molecules for which the inner turning point of the Rydberg electron on the radial plus centrifugal potential lies outside the bulk of the ion core electron density are known as core-non-penetrating states. Interpretation
of Rydberg spectroscopic data for polar molecules makes use of effective potentials that include ionic bonding and polarizability in order to represent electric properties of the ion core. We examine the accuracy and convergence properties of
single-center polarization potentials and show that the center of charge representation, for which the core dipole moment
is zero so that first-order l-mixing can be neglected, is excluded by the convergence sphere for use with l-states that can be
treated by an expansion about the center or mass, the center of dipole or a newly-defined center of polarizability. The potential
expansion converges only outside a sphere enclosing the charge distribution, and the sphere is much larger when the center of
charge is used. For higher l-states of the rotating molecule (turning points defined in center of mass), the sphere required for
convergence is much smaller for an origin within the charge distribution, so that lower l states are modeled correctly.
3:53 – 4:08
+
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ELECTRONIC STRUCTURE OF THE X Σ ION CORE OF CaF RYDBERG STATES
STEPHEN COY, JOSHUA H BARABAN, DAVID GRIMES, TIMOTHY J BARNUM, ROBERT W FIELD,
Department of Chemistry, MIT, Cambridge, MA, USA; BRYAN M. WONG, Department of Chemistry, University
of California, Riverside, Riverside, Ca, USA.
We use ab-initio calculations to examine the electronic structure of CaF+ ,making comparison to the available experimental data and effective potential models. An electron-density-difference plot comparing isolated Ca+2 and F− ions with
the CaF+ ab-initio density shows s-d mixing at Ca, and maintenance of near spherical symmetry at F. This unexpected result
is interpreted in terms of the electronic states of Ca+ . Calculation of the effective charge on F spanning the region of the
transition from ionic to dissociating Ca+ F0 locates the transition very near the crossing of the Ca+2 F− and Ca+ F0 curves
and additionally determines the width of the ionic-bonding transition region. An accurate non-relativistic long or intermediate range effective potential for the CaF Rydberg electron is obtained by choice of origin at the center of polarizability,
with inclusion of multipoles through octopole and the use of anisotropic polarizability. The estimates of CaF+ polarizability
from ab-initio and effective potential models predict high anisotropy, with the parallel dipole polarizability, where the atomic
dipoles are mutually enhancing, predicted to be about double the perpendicular polarizability, where the atomic dipoles are
mutually antagonistic.
TJ10
4:10 – 4:25
SYSTEMATICS OF RYDBERG SERIES OF DIATOMIC MOLECULES AND CORRELATION DIAGRAMS
CHUN-WOO LEE, Chemistry, Ajou University, Suwon, Republic of Korea.
Rydberg states are studied for H2 , Li2 , HeH, LiH and BeH using the multi-reference configuration interaction (MRCI)
method. The systematics and regularities of the physical properties such as potential energies curves (PECs), quantum defect
curves, permanent dipole moment and transition dipole moment curves of the Rydberg series are studied. They are explained
using united atom perturbation theory by Bingel and Byers-Brown, Fermi model, Stark theory, and Mulliken’s theory. Interesting mirror relationships of the dipole moments are observed between l-mixed Rydberg series, indicating that the members
of the l-mixed Rydberg series have dipole moments with opposite directions, which are related to the reversal of the polarity
of a dipole moment at the avoided crossing points. The assignment of highly excited states is difficult because of the usual
absence of the knowledge on the behaviors of potential energy curves at small internuclear separation whereby the correlation between the united atom limit and separated atoms limit cannot be given. All electron MRCI calculations of PECs are
performed to obtain the correlation diagrams between Rydberg orbitals at the united-atom and separated atoms limits.
124
TJ11
INVITED TALK
4:27 – 4:42
OBSERVATION OF CS TRILOBITE MOLECULES WITH KILO-DEBYE MOLECULAR FRAME PERMANENT ELECTRIC DIPOLE MOMENTS
ar
y
JAMES P SHAFFER, Homer L Dodge Department of Physics and Astronomy, University of Oklahoma, Norman,
OK, USA.
in
We present results on Cs ultracold Rydberg atom experiments involving trilobite and butterfly molecules. Trilobite
molecules are predicted to have giant, body-fixed permanent dipole moments, on the order of 1000 Debye. We present
spectra for nS1/2 +6S1/2 3 Σ+ molecules, where n=37, 39 and 40, and measurements of the Stark broadenings of selected
trilobite states in Cs due to the application of a constant external electric field. These results show that for Cs, because
of its near integer s-state quantum defect, it is possible to photoassociate molecules whose wavefunction is predominantly
of trilobite character yielding molecular frame dipole moments of around 2000 Debye. In addition, we have also recently
observed states whose spectra show characteristics of p-wave dominated butterfly states. The work on what we believe to be
the butterfly states will be compared and contrasted to the measurements of the trilobite states.
TJ12
4:44 – 4:59
MOLECULE FORMATION AND STATE-CHANGING COLLISIONS OF SINGLE RYDBERG ATOMS IN A BEC
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KATHRIN SOPHIE KLEINBACH, MICHAEL SCHLAGMÜLLER, TARA CUBEL LIEBISCH, KARL MAGNUS WESTPHAL, FABIAN BÖTTCHER, ROBERT LÖW, SEBASTIAN HOFFERBERTH, TILMAN PFAU,
5. Physikalisches Institut, Universität Stuttgart, Stuttgart, Germany; JESÚS PÉREZ-RÍOS, C. H. GREENE,
Department of Physics, Purdue University, West Lafayette, IN, USA.
A single Rydberg excitation in the high-density and low-temperature environment of a Bose-Einstein condensate (BEC)
leads to a fascinating testbed of low-energy electron-neutral and ion-neutral scattering. In particular the small interparticle
spacing in a BEC makes it possible to study the role of ion-neutral interactions in l-changing collisions on time scales much
shorter than the Rydberg lifetime. We take advantage of the mean field density shift, caused by elastic electron-neutral
collisions, to probe density dependent shells of the 87 Rb BEC and thereby measure the l-changing collision time versus
density and principal quantum number. We report on l-changing collisions due to inelastic scattering of the Rydberg electron
with a neutral atom located near the Rydberg ionic core. We measure timescales of both the l-changing collision and the
Rb2 molecule formation of less than one microsecond for n < 100 at the highest BEC densities. We extract a change in
kinetic energy of the Rydberg atoms that matches well with the energy gap to the next-lowest manifold. We measure Rb2
signal that decreases with increasing principal quantum number. The mechanism and timescales of the l-changing collision
are compared with simulations including the motion of the ionic core and neutral atoms, as well as the Rydberg electron.
TJ13
RYDBERG, VALENCE AND ION-PAIR QUINTET STATES OF O2
5:01 – 5:16
GABRIEL J. VAZQUEZ, Instituto de Ciencias Fisicas, Universidad Nacional Autonoma de Mexico (UNAM),
Cuernavaca, Morelos, Mexico; HANS P. LIEBERMANN, Fachbereich C-Physikalische und Theoretische
Chemie, Bergische Universität Wuppertal, Wuppertal, Germany; H. LEFEBVRE-BRION, Institut des Sciences
Moléculaires d’Orsay, Université Paris-Sud, Orsay, France.
We carried out a relatively comprehensive ab–initio study of the electronic structure of O2 and O+
2 . We employed the
MRD–CI package together with the cc–pV4Z basis set augmented with seven diffuse functions of s, p and d character on
each atom. In this contribution we focus on the quintet states. Potential energy curves of about 50 quintet states were
5 − 5 − 5
5
5
computed. The spectroscopic constants of the six valence quintet states (5 Σ+
g , Σg , Σu , Πu , Πg , ∆g ) dissociating to
3
3
5 − 5 − 5
the first dissociation limit O( P)+O( P) are reported. The four ion–pair quintet states ( Σg , Σu , Πg ,5 Πu ) dissociating
into O+ (4 S)+O− (2 P) at 17.28 eV were also computed and their spectroscopic constants will be presented. A number of
+
4
6 +
bound quintet Rydberg states belonging to series converging to the a4 Πu , b4 Σ−
g , f Πg and Σu states of the O2 cation were
identified and attributed. Long–range interactions involving the ion–pair states as they slowly approach their dissociation
limit will be shown.
125
TJ14
′
AB INITIO STUDY OF THE H, J, I, I AND I
′′ 3
5:18 – 5:33
Πu SUPEREXCITED STATES OF O2
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GABRIEL J. VAZQUEZ, Instituto de Ciencias Fisicas, Universidad Nacional Autonoma de Mexico (UNAM),
Cuernavaca, Morelos, Mexico; HANS P. LIEBERMANN, Fachbereich C-Physikalische und Theoretische
Chemie, Bergische Universität Wuppertal, Wuppertal, Germany; H. LEFEBVRE-BRION, Institut des Sciences
Moléculaires d’Orsay, Université Paris-Sud, Orsay, France.
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In this presentation we report progress in the computation of superexcited states of O2 , namely, of bound 3 Πu Rydberg
3
states of the neutral molecule converging to the a4 Πu state of O+
2 . Up to twenty Πu potential energy curves were computed.
The MRD–CI package together with the cc–pV4Z basis set augmented with seven diffuse functions of s, p and d type on
each atom were employed. This study was prompted by the demand of potential curves to try to understand the mechanism
of the neutral dissociation of O2 above the first ionization limit (IP= 12.07 eV) where there exists a competition between
autoionization and predissociation. This undertaking focuses on the computation of the I, I′ and I′′ 3 Πu states that have been
postulated as involved in the neutral dissociation of O2 in the 865–790 Å (14.33–15.69 eV) energy region.
126
WA. Plenary
Wednesday, June 24, 2015 – 8:30 AM
RAO AWARDS
Presentation of Awards by Yunjie Xu, University of Alberta
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Chair: Leslie Looney, University of Illinois, Urbana, IL, USA
8:30
8:40
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MILLER PRIZE
Introduction by Mike Heaven, Emory University
in
2014 Rao Award Winners
Grant Buckingham, University of Colorado
Kathryn Chew, Yale University
Yu-Hsuan Huang, National Chiao Tung University
WA01
8:45 – 9:00
INFRARED LASER STARK SPECTROSCOPY OF THE OH···CH3 OH COMPLEX ISOLATED IN SUPERFLUID HELIUM DROPLETS
CHRISTOPHER M. LEAVITT, JOSEPH T. BRICE, GARY E. DOUBERLY, Department of Chemistry, University of Georgia, Athens, GA, USA; FEDERICO J HERNANDEZ, GUSTAVO A PINO, INFIQC (CONICET –
Universidad Nacional de Córdoba) Dpto. de Fisicoquı́mica – Facultad de Ciencias Quı́, Universidad Nacional
de Córdoba, Ciudad Universitaria, Córdoba, Argentina.
The elimination of volatile organic compounds (VOCs) from the atmosphere is initiated by reactions with OH, NO3 and
O3 .a,b For oxygenated VOCs, such as alcohols, ketones, ethers, etc., reactions occur nearly exclusively with the hydroxyl
radical. Furthermore, the potential energy surfaces associated with reactions between OH and oxygenated VOCs generally
feature a pre-reactive complex, stabilized by hydrogen bonding, which results in rate constants that exhibit large negative
temperature dependencies.c This was explicitly demonstrated recently for the OH + methanol (MeOH) reaction, where the
rate constant increased by nearly two orders of magnitude when the temperature decreased from 200 K to below 70 K,
highlighting the potential impact of this reaction in the interstellar medium (ISM).d,e In this study, we trap this postulated
pre-reactive complex formed between OH and MeOH using He nanodroplet isolation (HENDI) techniques, and probe this
species using a combination of mass spectrometry and infrared laser Stark spectroscopy.
a
Atkinson, R.; Arey, J., Chem. Rev. 2003, 103, 4605-4638.
Mellouki, A.; Le Bras, G.; Sidebottom, H., Chem. Rev. 2003, 103, 5077-5096.
Smith, I. W. M.; Ravishankara, A. R., J. Phys. Chem. A 2002, 106, 4798-4807
d
Shannon, R. J.; Blitz, M. A.; Goddard, A.; Heard, D. E., Nat. Chem. 2013, 5, 745-749.
e
Martin, J. C. G.; Caravan, R. L.; Blitz, M. A.; Heard, D. E.; Plane, J. M. C., J. Phys. Chem. A 2014, 118, 2693-2701.
b
c
FLYGARE AWARDS
Introduction by Trevor Sears, Brookhaven National Laboratory
9:05
127
WA02
WHAT CAN WE EXPECT OF HIGH-RESOLUTION SPECTROSCOPIES ON CARBOHYDRATES?
9:10 – 9:25
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EMILIO J. COCINERO, PATRICIA ECIJA, ICIAR URIARTE, IMANOL USABIAGA, JOSÉ A.
FERNÁNDEZ, FRANCISCO J. BASTERRETXEA, Departamento de Quı́mica Fı́sica, Universidad del
Paı́s Vasco (UPV-EHU), Bilbao, Spain; ALBERTO LESARRI, Departamento Quı́mica Fı́sica y Quı́mica
Inorgánica , Universidad de Valladolid, Valladolid, Spain; BENJAMIN G. DAVIS, Department of Chemistry,
Oxford University, Oxford, United Kingdom.
a
in
Carbohydrates are one of the most multifaceted building blocks, performing numerous roles in living organisms. We present several structural investigations on carbohydrates exploiting an experimental strategy which combines
microwave (MW) and laser spectroscopies in high-resolution. Laser spectroscopy offers high sensitivity coupled to mass and conformer selectivity,
making it ideal for polysaccharides studies. On the other hand, microwave
spectroscopy provides much higher resolution and direct access to molecular
structure of monosaccharides. This combined approach provides not only accurate chemical insight on conformation, structure and molecular properties,
but also benchmarking standards guiding the development of theoretical calculations.
In order to illustrate the possibilities of a combined MW-laser approach we present results on the conformational landscape and structural properties of several monosaccharidesa,b and oligosaccharides including microsolvation and molecular
recognition processes of carbohydrates.c,d
E.J. Cocinero, A. Lesarri, P. Écija, F.J. Basterretxea, J.-U. Grabow, J.A. Fernández and F. Castaño Angew. Chem. Int. Ed. 51, 3119-3124, 2012.
E.J. Cocinero, A. Lesarri, P. Écija, Á. Cimas, B.G. Davis, F.J. Basterretxea, J.A. Fernández and F. Castaño J. Am. Chem. Soc. 135, 2845-2852, 2013.
E.J. Cocinero, P. Çarçabal, T.D. Vaden, J.P. Simons and B.G. Davis Nature 469, 76-80, 2011.
d
C.S. Barry, E.J. Cocinero, P. Çarçabal, D.P. Gamblin, E.C. Stanca-Kaposta, S. M. Fernández-Alonso, S. Rudić, J.P. Simons and B.G. Davis J. Am. Chem. Soc. 135,
16895-16903, 2013.
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c
WA03
9:30 – 9:45
CONSTRUCTION OF POTENTIAL ENERGY SURFACES FOR THEORETICAL STUDIES OF SPECTROSCOPY AND
DYNAMICS
RICHARD DAWES, Department of Chemistry, Missouri University of Science and Technology, Rolla, MO, USA.
Accurate potential energy surfaces (PESs) combined with methods to solve the Schrödinger equation for the nuclei permit
the prediction and interpretation of various types of molecular spectra and/or dynamics.
Part of this talk describes the development of a PES generator (software code) which uses parallel processing on HighPerformance Computing (HPC) clusters to construct PESs automatically. Thousands of ab initio data are computed at geometries chosen by an algorithm and fit to a functional form. This strategy is particularly successful when the electronic structure
is robustly convergent (such as vdWs systems composed of two closed-shell monomers). Results for a few of such systems
[e.g., (CO)2 , (NNO)2 , CO2 -CS2 , (OCS)2 ] will be presented.
The electronic structure of molecules is difficult to describe continuously across global reactive PESs since it changes
qualitatively as bonds are formed and broken along reaction coordinates. I will discuss a high-level ab initio method (GDWSA-CASSCF/MRCI) designed to allow the electronic wavefunction to smoothly evolve across the PES and provide an accurate and balanced description of the various regions. These methods are combined to study a number of small gas-phased
molecules from the areas of atmospheric, combustion and interstellar chemistry including a large variational calculation of all
the bound vibrational states of ozone and the photodissociation dynamics of the simplest Criegee intermediate (CH2 OO).
Intermission
128
WA04
10:35 – 10:50
1
MILLIMETER AND SUBMILLIMETER STUDIES OF O( D) INSERTION REACTIONS TO FORM MOLECULES OF
ASTROPHYSICAL INTEREST
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BRIAN HAYS, NADINE WEHRES, BRIDGET ALLIGOOD DEPRINCE, ALTHEA A. M. ROY, JACOB
LAAS, SUSANNA L. WIDICUS WEAVER, Department of Chemistry, Emory University, Atlanta, GA, USA.
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While both the number of detected interstellar molecules and their chemical complexity continue to increase, understanding of the processes leading to their formation is lacking. Our research group combines laboratory spectroscopy, observational
astronomy, and astrochemical modeling for an interdisciplinary examination of the chemistry of star and planet formation.
This talk will focus on our laboratory studies of O(1 D) insertion reactions with organic molecules to produce molecules of
astrophysical interest. By employing these reactions in a supersonic expansion, we are able to produce interstellar organic
reaction intermediates that are unstable under terrestrial conditions; we then probe the products using millimeter and submillimeter spectroscopy. We benchmarked this setup using the well-studied O(1 D) + methane reaction to form methanol. After
optimizing methanol production, we moved on to study the O(1 D) + ethylene reaction to form vinyl alcohol (CH2 CHOH),
and the O(1 D) + methyl amine reaction to form aminomethanol (NH2 CH2 OH). Vinyl alcohol measurements have now been
extended up to 450 GHz, and the associated spectral analysis is complete. A possible detection of aminomethanol has also
been made, and continued spectral studies and analysis are underway. We will present the results from these experiments and
discuss future applications of these molecular and spectroscopic techniques.
WA05
10:55 – 11:10
TERAHERTZ AND INFRARED LABORATORY SPECTROSCOPY IN SUPPORT OF NASA MISSIONS
SHANSHAN YU, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, USA.
The JPL molecular spectroscopy group supports NASA programs encompassing Astrophysics, Atmospheric Science, and
Planetary Science. Ongoing activities include measurement and analysis of molecular spectra in the terahertz and infrared
regions under conditions akin to the remote environments under study in NASA missions. This presentation will show the implementation of state-of-the-art spectroscopic techniques to fulfill spectroscopic demands of the Herschel Space Observatorya
and the Orbiting Carbon Observatory re-flight (OCO-2)b .
A demonstrative example of the significantly improved frequency predictions for the H3 O+ ground state high-J transitions will be given. This work was critical to Herschel’s successful identification of highly excited metastable H3 O+ Terahertz
lines with J = K up to 11, one of the Herschel mission’s many surprising observational results. The observation and subsequent laboratory work revealed that (1) these highly excited H3 O+ lines had already been observed by European Southern
Observatory’s Atacama Pathfinder Experiment telescope a few years before but had been classified as U-lines; (2) the H3 O+
number density was previously underestimated by an order of magnitude, due to ignorance of the population in the metastable
states.
A second example focuses on O2 , an important absorber from the microwave through the deep UV. This work is motivated
by the challenge of developing an accurate and complete spectroscopic characterization of molecular oxygen across a wide
frequency range for current and planned Earth atmospheric observations. Especially, OCO-2 utilizes the O2 A-band for
air mass calibration; extremely accurate O2 molecular data, i.e., line positions with uncertainty on the order of MHz for
the A-band around 13000 cm−1 , are required to fulfill the demand of the proposed 0.25% precision for the carbon dioxide
concentration retrievals.
a
b
G. Pilbratt, J. Riedinger, T. Passvogel, G. Crone, D. Doyle, U. Gageur et al. A&A, 518, L1 (2010).
D. Crisp, B.M Fisher, C. O’Dell, C. Frankenberg, R. Basilio, H. Boesch et al., Atmos. Meas. Tech. 5, 687-707 (2012).
COBLENTZ AWARD
Presentation of Award by Mark Druy, Coblentz Society
11:15
129
WA06
Coblentz Society Award Lecture
11:20 – 12:00
LASER SPECTROSCOPY OF RADICALS, CARBENES, AND IONS IN SUPERFLUID HELIUM DROPLETS
GARY E. DOUBERLY, Department of Chemistry, University of Georgia, Athens, GA, USA.
a
in
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The first beam of helium droplets was reported in the 1961 paper
Strahlen aus kondensiertem Helium im Hochvakuum by Von E. W. Becker
and co-workers.a However, molecular spectroscopy of helium-solvated
dopants wasn’t realized until 30 years later in the laboratories of Scoles and
Toennies.b,c It has now been two decades since this early, seminal work on
doped helium droplets, yet the field of helium droplet spectroscopy is still
fresh with vast potential. Analogous in many ways to cryogenic matrix isolation spectroscopy, the helium droplet is an ideal environment to spectroscopically probe difficult to prepare molecular species, such as radicals, carbenes
and ions. The quantum nature of helium at 0.35 K often results in molecular
spectra that are sufficiently resolved to evoke an analysis of line shapes and
fine-structure that is worthy of the International Symposium on Molecular Spectroscopy. The present talk will focus on our
recent successful attempts to efficiently dope the title molecular species into helium droplets and probe their properties with
infrared laser Stark and Zeeman spectroscopies.
E. W. Becker, R. Klingelhöfer, P. Lohse, Z. Naturforsch. A 16A, 1259 (1961).
S. Goyal, D. L. Schutt, G. Scoles, Phys. Rev. Lett. 69, 933 (1992).
c
M. Hartmann, R. E. Miller, J. P. Toennies, A. F. Vilesov, Phys. Rev. Lett. 75, 1566 (1995).
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130
WF. Mini-symposium: High-Precision Spectroscopy
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Chair: Kevin Cossel, JILA - University of Colorado, Boulder, CO, USA
WF01
INVITED TALK
ULTRASENSITIVE, HIGH ACCURACY MEASUREMENTS OF TRACE GAS SPECIES
1:30 – 2:00
in
DAVID A. LONG, ADAM J. FLEISHER, Material Measurement Laboratory, National Institute of Standards
and Technology, Gaithersburg, MD, USA; DAVID F. PLUSQUELLIC, Physical Measurement Laboratory, National Institute of Standards and Technology, Boulder, CO, USA; JOSEPH HODGES, Material Measurement
Laboratory, National Institute of Standards and Technology, Gaithersburg, MD, USA.
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Our laboratory seeks to apply novel cavity-enhanced spectroscopic techniques to present problems in atmospheric and
physical chemistry. Primarily we use cavity ring-down spectroscopy in which the passive decay of optical power within a
Fabry-Pérot resonator is utilized to extract an absorption signal. With this technique we have demonstrated quantum (shot)
noise limited sensitivities in both the near-infrared and mid-infrared spectral regions. Both commercial and home-built optical
frequency combs are employed either to serve as absolute frequency references for molecular spectra or in a multiheterodyne
approach for multiplexed sensing. I will discuss this novel instrumentation as well as measurements we have made of atmospherically relevant species such as CO2 , H2 O, O2 , CH4 , and CO with implications for in situ and remote (i.e. satellite-based)
sensing. I will conclude by discussing future directions and plans for challenging measurements in the mid-infrared.
WF02
2:05 – 2:20
PROBING BUFFER-GAS COOLED MOLECULES WITH DIRECT FREQUENCY COMB SPECTROSCOPY IN THE
MID-INFRRARED
BEN SPAUN, BRYAN CHANGALA, BRYCE J BJORK, OLIVER H HECKL, JILA, National Institute of Standards and Technology and Univ. of Colorado Department of Physics, University of Colorado, Boulder, CO, USA;
DAVID PATTERSON, JOHN M. DOYLE, Department of Physics, Harvard University, Cambridge, MA, USA;
JUN YE, JILA, National Institute of Standards and Technology and Univ. of Colorado Department of Physics,
University of Colorado, Boulder, CO, USA.
We present the first demonstration of cavity-enhanced direct frequency comb spectroscopya on buffer-gas cooled
moleculesb . By coupling a mid-infrared frequency comb to a high-finesse cavity surrounding a helium buffer-gas chamber,
we can gather rotationally resolved absorption spectra with high sensitivity over a broad wavelength region. The measured
∼10 K rotational and translational temperatures of buffer-gas cooled molecules drastically simplify the observed spectra,
compared to those of room temperature molecules, and allow for high spectral resolution limited only by Doppler broadening
(10-100 MHz). Our system allows for the extension of high-resolution spectroscopy to larger molecules, enabling detailed
analysis of molecular structure and dynamics, while taking full advantage of the powerful optical properties of frequency
combs.
a
A. Foltynowicz et al. Cavity-enhanced optical frequency comb spectroscopy in the mid-infrared application to trace detection of hydrogen peroxide. Applied Physics B, vol.
110, pp. 163–175, 2013.
b
D. Patterson and J. M. Doyle. Cooling molecules in a cell for FTMW spectroscopy. Molecular Physics 110, 1757–1766, 2012.
131
WF03
FREQUENCY-AGILE DIFFERENTIAL CAVITY RING-DOWN SPECTROSCOPY
2:22 – 2:37
ZACHARY REED, JOSEPH HODGES, Chemical Sciences Division, National Institute of Standards and Technology, Gaithersburg, MD, USA.
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The ultimate precision of highly sensitive cavity-enhanced spectroscopic measurements is often limited by interferences
(etalons) caused by weak coupled-cavity effects. Differential measurements of ring-down decay constants have previously
been demonstrated to largely cancel these effects, but the measurement acquisition rates were relatively low [1,2]. We
have previously demonstrated the use of frequency agile rapid scanning cavity ring-down spectroscopy (FARS-CRDS) for
acquisition of absorption spectra [3]. Here, the method of rapidly scanned, frequency-agile differential cavity ring-down
spectroscopy (FADS-CRDS) is presented for reducing the effect of these interferences and other shot-to-shot statistical
variations in measured decay times. To this end, an electro-optic phase modulator (EOM) with a bandwidth of 20 GHz
is driven by a microwave source, generating pairs of sidebands on the probe laser. The optical resonator acts as a highly
selective optical filter to all laser frequencies except for one tunable sideband. This sideband may be stepped arbitrarily from
mode-to-mode of the ring-down cavity, at a rate limited only by the cavity buildup/decay time. The ability to probe any cavity
mode across the EOM bandwidth enables a variety of methods for generating differential spectra. The differential mode
spacing may be changed, and the effect of this method on suppressing the various coupled-cavity interactions present in the
system is discussed. Alternatively, each mode may also be differentially referenced to a single point, providing immunity to
temporal variations in the base losses of the cavity while allowing for conventional spectral fitting approaches. Differential
measurements of absorption are acquired at 3.3 kHz and a minimum detectable absorption coefficient of 5 x10−12 cm−1 in 1
s averaging time is achieved.
1. J. Courtois, K. Bielska, and J.T Hodges J. Opt. Soc. Am. B, 30, 1486-1495, 2013
2. H.F. Huang and K.K. Lehmann App. Optics 49, 1378-1387, 2010
3. G.-W. Truong, K.O. Douglass, S.E. Maxwell, R.D. van Zee, D.F. Plusquellic, J.T. Hodges, and D.A. Long Nature
Photonics, 7, 532-534, 2013
WF04
QUANTUM-NOISE-LIMITED CAVITY RING-DOWN SPECTROSCOPY IN THE MID-INFRARED
2:39 – 2:54
ADAM J. FLEISHER, DAVID A. LONG, QINGNAN LIU, JOSEPH HODGES, Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD, USA.
We report a highly sensitive mid-infrared spectrometer capable of recording cavity ring-down events in the quantum
(shot) noise limit. A linear optical cavity of finesse 31,000 was pumped by a distributed feedback quantum cascade laser
(DFB-QCL) operating at 4.5 µm until a cavity transmission threshold was reached. A fast optical switch then extinguished
optical pumping and initiated a cavity decay which exhibited root-mean-square noise proportional to the square root of
optical power (quantum noise) for several cavity time constants until a detector noise floor was reached. This spectrometer
has achieved a noise-equivalent absorption of NEA = 2.6 × 10−11 cm−1 Hz−1/2 and a minimum absorption coefficient of
α = 2.3×10−11 cm−1 in 3 seconds. Applications for such a highly sensitive spectrometer operating in the mid-infrared region,
including ultra-trace molecular spectroscopy of CO2 isotopologues and the direct interrogation of weak mirror birefringence
and polarization-dependent losses, will be discussed.
132
WF05
2:56 – 3:11
MOLECULAR LINE PARAMETERS PRECISELY DETERMINED BY A CAVITY RING-DOWN SPECTROMETER
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SHUI-MING HU, YAN TAN, JIN WANG, YAN LU, CUNFENG CHENG, YU ROBERT SUN, AN-WEN LIU,
Hefei National Laboratory for Physical Science at Microscale, University of Science and Technology of China,
Hefei, China.
in
A cavity ring-down spectrometer calibrated with a set of precise atomic lines was built to retrieve precise line parameters
in the near infrared. [1,2] The spectrometer allows us to detect absorptions with a sensitivity of 10−11 cm−1 and a spectral
precision up to 10−6 cm−1 . Ro-vibrational lines in the second overtone of H2 have been observed, including the extremely
weak S3 (5) line with a line intensity less than 1×10−30 cm/molecule, which is among the weakest molecular lines detected by
absorption in the gas phase. The absolute line positions of H2 agree well with the high-level quantum chemical calculations
including relativistic and QED corrections, with the deviation being less than 5 × 10−4 cm−1 . [3,4] A quantitative study has
also been carried out on the ν1 + 5ν3 band of CO2 . [5] It was the first CO2 band observed 80 years ago in the spectrum of
Venus. We determined the line positions with an accuracy of 3 × 10−5 cm−1 , two orders of magnitude better than previous
studies. Similar studies have been carried out to determine the line parameters of H2 O [6] and CO [7] in the spectral regions
near 0.8 µm. The spectroscopic parameters can be used in varies studies, from the atmospheres of the earth-like planets to the
test of fundamental physics.
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References
[1] H. Pan, et al. Rev. Sci. Instrum. 82, 103110 (2011).
[2] C.-F. Cheng, Opt. Expr. 20, 9956 (2012).
[3] C.-F. Cheng, et al. Phys. Rev. A 85, 024501 (2012).
[4] y. Tan, et al. J. Mol. Spectrosc. 300, 60 (2014).
[5] Y. Lu, et al. Astrophys. J. 775, 71 (2013).
[6] Y. Lu, et al. JQSRT 118, 96 (2013).
[7] Y. Tan, et al. “Ro-vibrational analysis of the fifth overtone of CO at 802 nm”, under preparation.
WF06
3:13 – 3:23
BROADBAND COMB-RESOLVED CAVITY ENHANCED SPECTROMETER WITH GRAPHENE MODULATOR
KEVIN LEE, CHRISTIAN MOHR, JIE JIANG, MARTIN FERMANN, Laser Research, IMRA AMERICA, Inc,
Ann Arbor, MI, USA; CHIEN-CHUNG LEE, THOMAS R SCHIBLI, Department of Physics, University of
Colorado, Boulder, CO, USA; GRZEGORZ KOWZAN, PIOTR MASLOWSKI, Institute of Physics, Faculty
of Physics, Astronomy and Informatics, Nicolaus Copernicus University, Torun, Poland.
Optical cavities enhance sensitivity in absorption spectroscopy. While this is commonly done with single wavelengths,
broad bandwidths can be coupled into the cavity using frequency combs. The combination of cavity enhancement and broad
bandwidth allows simultaneous measurement of tens of transitions with high signal-to-noise for even weak near-infrared
transitions. This removes the need for time-consuming sequencing acquisition or long-term averaging, so any systematic
errors from long-term drifts of the experimental setup or slow changes of sample composition are minimized. Resolving comb
lines provides a high accuracy, absolute frequency axis. This is of great importance for gas metrology and data acquisition
for future molecular lines databases, and can be applied to simultaneous trace-gas detection of gas mixtures.
Coupling of a frequency comb into a cavity can be complex, so we introduce and demonstrate a simplification. The
Pound-Drever-Hall method for locking a cavity and a frequency comb together requires a phase modulation of the laser
output. We use the graphene modulator that is already in the Tm fiber laser cavity for controlling the carrier envelope offset
of the frequency comb, rather than adding a lossy external modulator. The graphene modulator can operate at frequencies of
over 1 MHz, which is sufficient for controlling the laser cavity length actuator which operates below 100 kHz.
We match the laser cavity length to fast variations of the enhancement cavity length. Slow variations are stabilized by
comparison of the pulse repetition rate to a GPS reference. The carrier envelope offset is locked to a constant value chosen
to optimize the transmitted spectrum. The transmitted pulse train is a stable frequency comb suitable for long measurements,
including the acquisition of comb-resolved Fourier transform spectra with a minimum absorption coefficient of about 2×10−7
cm−1 . For our 38 cm long enhancement cavity, the comb spacing is 394 MHz. With our 300 cm−1 bandwidth at 2 µm, we
simultaneously measure the full comb line resolved CO2 vibrational manifold at 4850 cm−1 . Other spectral ranges can be
accessed by using graphene with different gain fibers or nonlinear frequency conversion.
Intermission
133
WF07
INVITED TALK
DUAL-COMB SPECTROSCOPY IN THE OPEN AIR
3:42 – 4:12
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GREG B RIEKER, Department of Mechanical Engineering, University of Colorado Boulder, Boulder, CO, USA;
ANDREW KLOSE, SCOTT DIDDAMS, Time and Frequency Division, National Institute of Standards and Technology, Boulder, CO, USA; IAN CODDINGTON, FABRIZIO GIORGETTA, LAURA SINCLAIR, ESTHER
BAUMANN, GAR-WING TRUONG, GABRIEL YCAS, WILLIAM C SWANN, NATHAN R. NEWBURY,
Quantum Electronics and Photonics Division, National Institute of Standards and Technology, Boulder, CO,
USA.
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Dual-comb spectroscopy is arguably the natural successor to FTIR. Based on the interference between two frequency
combs, this technique can record broadband spectra with a resolution better than 0.0003 cm−1 . Like FTIR, dual-comb
spectroscopy measures an entire spectrum simultaneously, allowing for suppression of systematic errors related to temporal
dynamics of the sample. Unlike FTIR it records the entire spectrum with virtually no instrument lineshape or error in the
frequency axis. The lack of moving parts in dual-comb spectroscopy means that spectra can be recorded in milliseconds
to microseconds with the desired signal-to-noise being the only real constrain on the minimum recording time. Finally the
high spacial beam quality of the frequency combs allows for increased sensitivity through long interaction paths either in
free-space, multi-pass cells or enhancement cavities.
This talk will explore the recent use of dual-comb spectroscopy in the near-infrared to measure atmospheric carbon
dioxide, methane and water concentrations over a 2-km outdoor open-air path. Due to many of the strengths just mentioned,
precisions of <1 ppm for CO2 and <3 ppb for CH4 in 5 min are achieved making this system very attractive for carbon
monitoring at length scales relevant to carbon transport models.
Additionally this presentation will address recent work on robust, compact, and portable dual-comb spectrometers as
well as dual-comb spectroscopy further into the IR.
WF08
4:17 – 4:32
FREQUENCY-COMB REFERENCED SPECTROSCOPY OF ν4 AND ν5 HOT BANDS IN THE ν1 +ν3 COMBINATION
BAND OF C2 H2
SYLVESTRE TWAGIRAYEZU, Department of Chemistry, Brookhaven National Laboratory, Upton, NY, USA;
MATTHEW CICH, Department of Chemistry, Stony Brook University, Stony Brook, NY, USA; TREVOR
SEARSa , Chemistry Department, Brookhaven National Laboratory, Upton, NY, USA; C. McRAVEN, Am
Klopfersptiz 19a, Menlo Systems, GmbH, 82152 Martinsried, Germany; GREGORY HALL, Chemistry Department, Brookhaven National Laboratory, Upton, NY, USA.
Doppler-free transition frequencies for ν4 and ν5 hot bands in the band of C2 H2 have been measured using saturation dip
spectroscopy with an extended cavity diode laser referenced to a frequency comb. The frequency accuracy of the measured
transitions, as judged from line shape model fits and the spectrometer stability, is better than 30 kHz. This is some 2-3 orders
of magnitude improvement on the accuracy and precision of previous measurements of the line positions derived from the
analysis of high-resolution Fourier transform infrared absorption spectra. The data were analyzed by determining the upper
state energies, using known lower state level positions, and fitting them to a J(J + 1) polynomial expansion to identify
perturbations. The results reveal that the upper rotational energy level structure is mostly regular but suffers J−localized
perturbations causing level shifts between one and several hundred MHz. These perturbations are due to accidental near
degeneracies with energy levels of the same J and larger bending vibrational excitation.
Acknowledgements: We are most grateful to Prof. D.S Perry (U. of Akron) and Prof. M. Herman (U. Libre de Bruxelles)
for providing us with detailed results from their work and helpful discussions. Work at Brookhaven National Laboratory is
funded by the Division of Chemical Sciences, Geosciences and Biosciences within the Offices of Basic Energy Sciences,
Office of Sciences, U.S. Department of Energy under Contract Nos. DE-AC02-98CH10886 and DE-SC0012704.
a
Also: Department of Chemistry, Stony Brook University, Stony Brook, NY 11794.
134
WF09
4:34 – 4:49
LOCAL PERTURBATIONS IN THE (10110) AND (10101) LEVELS OF C2 H2 FROM FREQUENCY COMBREFERENCED SPECTROSCOPY
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TREVOR SEARSa , Chemistry Department, Brookhaven National Laboratory, Upton, NY, USA; SYLVESTRE
TWAGIRAYEZU, DAMIEN FORTHOMME, Department of Chemistry, Brookhaven National Laboratory, Upton, NY, USA; GREGORY HALL, Chemistry Department, Brookhaven National Laboratory, Upton, NY, USA;
MATTHEW CICH, Department of Chemistry, Stony Brook University, Stony Brook, NY, USA.
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In work reported by Twagirayezu et al. at this meeting, the rest frequencies of more than 100 lines in the ν4 and
ν5 hot bands in the ν1 + ν3 combination band of acetylene have been measured by saturation dip spectroscopy using an
extended cavity diode laser locked to a frequency comb. This work was orginally directed towards providing a set of accurate
frequencies for the hot band line positions to aid in modeling the lineshapes of the main lines in the band. In analyzing the
results, we find that many of the upper levels in the hot band transitions suffer small, and in some cases not so small, local
perturbations. These arise because of J-dependent near degeneracies between the title levels and background levels of the
same symmetry, mostly derived from zero order states involving multiple quanta of bending excitation. The vibration-rotation
levels at the energies in question have previously been modeled using a polyad-based Hamiltonianb and the present data can
be interpreted on the basis of this model, but they also provide information which can be used to refine the model, and point
to terms that may have previously been neglected. The most important result is that the high precision of the measurements
gives the opportunity to calibrate the effects of background levels associated with high bending quantum numbers and angular
momentun states that are otherwise very difficult to access.
Acknowledgments: We are most grateful to D. S Perry (U. Akron) and M. Herman (U. Libre de Bruxelles) for helpful
discussions. Work at Brookhaven National Laboratory is funded by the Division of Chemical Sciences, Geosciences and
Biosciences within the Offices of Basic Energy Sciences, Office of Sciences, U.S. Department of Energy under Contract Nos.
DE-AC02-98CH10886 and DE-SC0012704.
a
b
also: Chemistry Department, Stony Brook University, Stony Brook, New York 11794
M. Herman and D. S. Perry, Phys. Chem. Chem. Phys., 15, 9970-9993 (2013)
WF10
4:51 – 5:06
NOISE-IMMUNE CAVITY-ENHANCED OPTICAL HETERODYNE MOLECULAR SPECTROMETRY MODELLING
UNDER SATURATED ABSORPTION
PATRICK DUPRÉ, Laboratoire de Physico-Chimie de l’Atmosphère, Université du Littoral Côte d’Opale,
Dunkerque, France.
The Noise-Immune Cavity-Enhanced Optical Heterodyne Molecular Spectrometry (NICE-OHMS) is a modern technique
renowned for its ultimate sensitivity, because it combines long equivalent absorption length provided by a high finesse cavity,
and a detection theoretically limited by the sole photon-shot-noise. One fallout of the high finesse is the possibility to accumulating strong intracavity electromagnetic fields (EMF). Under this condition, molecular transitions can be easy saturated
giving rise to the usual Lamb dips (or hole burning). However, the unusual shape of the basically trichromatic EMF (due
to the RF lateral sidebands) induces nonlinear couplings, i.e., new crossover transitions. An analytical methodology will be
presented to calculate spectra provided by NICE-OHMS experiments. It is based on the solutions of the equations of motion
of an open two-blocked-level system performed in the frequency-domain (optically thin medium). Knowing the transition
dipole moment, the NICE-OHMS signals (“absorption-like” and “dispersion-like”) can be simulated by integration over the
Doppler shifts and by paying attention to the molecular Zeeman sublevels and to the EMF polarizationa . The approach has
been validated by discussion experimental data obtained on two transitions of C2 H2 in the near-infrared under moderated saturationb . One of the applications of the saturated absorption is to be able to simultaneously determine the transition intensity
and the density number while only one these 2 quantities can only be assessed in nonlinear absorption.
a
b
J. Opt. Soc. Am. B 32, 838 (2015)
Optics Express 16, 14689 (2008)
135
WF11
MAGNETIC SPIN-TORSION COUPLING IN METHANOL
5:08 – 5:23
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L. H. COUDERT, C. GUTLE, LISA, CNRS, Universités Paris Est Créteil et Paris Diderot, Créteil, France; T.
R. HUET, Laboratoire PhLAM, UMR 8523 CNRS - Université de Lille 1, Villeneuve d’Ascq, France; JENSUWE GRABOW, Institut für Physikalische Chemie und Elektrochemie, Gottfried-Wilhelm-Leibniz-Universität,
Hannover, Germany.
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The hyperfine structure of non-rigid molecules in which hyperfine coupling arises from equivalent nuclei that can be
exchanged by large amplitude motions is of great interest and lead to unexpected results. In the non-rigid (C2 D2 )2 and
(D2 O)2 dimers, the hyperfine structure arising for nondegenerate tunneling sublevels can be accounted for using an effective
quadrupole coupling Hamiltonian with the same coupling constant for all four deuterium atoms.a In the non-rigid species
CD3 COH and HCOOCH3 , the large amplitude torsional motion leads to hyperfine patterns which are qualitatively dependent
on the torsional symmetry of the levels.b The interaction between a large amplitude torsional motion and the hyperfine
coupling may also lead to a less known hyperfine effect, the so-called magnetic spin-torsion coupling, which was first studied
by Heuvel and Dymanusc and which has not yet been conclusively evidenced.
In this talk, the magnetic hyperfine structure of the non-rigid methanol molecule will be investigated experimentally
and theoretically. 13 hyperfine patterns were recorded using two molecular beam microwave spectrometers. These patterns,
along with previously recorded ones,c were analyzed in an attempt to evidence the effects of the magnetic spin-torsion
coupling. The theoretical approach setup to analyze the observed data accounts for the spin-torsion coupling, in addition
to the familiar magnetic spin-rotation and spin-spin couplings, and relies on symmetry considerations to build a hyperfine
coupling Hamiltonian and a spin-rotation-torsion wavefunction compatible with the Pauli exclusion principle.
In the talk, the results of the analysis will be presented. The hyperfine coupling parameters retrieved will be discussed
and we hope to be able to conclusively evidence the effects of the magnetic spin-torsion.
a
b
c
Bhattacharjee, Muenter, and Coudert, J. Chem. Phys. 97 (1992) 8850; and Stahl and Coudert, J. Mol. Spectrosc. 157 (1993) 161.
Coudert and Lopez, J. Mol. Spectrosc. 239 (2006) 135; and Tudorie, Coudert, Huet, Jegouso, and Sedes, J. Chem. Phys. 134 (2011) 074314.
Heuvel and Dymanus, J. Mol. Spectrosc. 45 (1973) 282 and ibid 47 (1973) 363.
WF12
SPIN-ROTATION HYPERFINE SPLITTINGS AT MODERATE TO HIGH J VALUES IN METHANOL
5:25 – 5:40
LI-HONG XU, Department of Physics, University of New Brunswick, Saint John, NB, Canada; JON T.
HOUGEN, Sensor Science Division, National Institute of Standards and Technology, Gaithersburg, MD, USA;
SERGEY BELOV, G YU GOLUBIATNIKOV, ALEXANDER LAPINOV, Microwave Spectroscopy, Institute
of Applied Physics, Nizhny Novgorod, Russia; V. ILYUSHIN, E. A. ALEKSEEV, A. A. MESCHERYAKOV,
Radiospectrometry Department, Institute of Radio Astronomy of NASU, Kharkov, Ukraine.
In this talk we present a possible explanation, based on torsionally mediated proton-spin-overall-rotation interaction
operators, for the surprising observation in Nizhny Novgorod several years agoa of doublets in some Lamb-dip sub-millimeterwave transitions between torsion-rotation states of E symmetry in methanol. These observed doublet splittings, some as large
as 70 kHz, were later confirmed by independent Lamb-dip measurements in Kharkov. In this talk we first show the observed
J-dependence of the doublet splittings for two b-type Q branches (one from each laboratory), and then focus on our theoretical
explanation. The latter involves three topics: (i) group theoretically allowed terms in the spin-rotation Hamiltonian, (ii) matrix
elements of these terms between the degenerate components of torsion-rotation E states, calculated using wavefunctions from
an earlier global fit of torsion-rotation transitions of methanol in the vt = 0, 1, and 2 statesb , and (iii) least-squares fits of
coefficients of these terms to about 35 experimentally resolved doublet splittings in the quantum number ranges of K = -2
to +2, J = 13 to 34, and vt = 0. Rather pleasing residuals are obtained for these doublet splittings, and a number of narrow
transitions, in which no doublet splitting could be detected, are also in agreement with predictions from the theory. Some
remaining disagreements between experiment and the present theoretical explanation will be mentioned.
a
G. Yu. Golubiatnikov, S. P. Belov, A. V. Lapinov, ”CH3 OH Sub-Doppler Spectroscopy,” (Paper MF04) and S.P. Belov, A.V. Burenin, G.Yu. Golubiatnikov, A.V. Lapinov,
”What is the Nature of the Doublets in the E-Methanol Lamb-dip Spectra?” (Paper FB07), 68th International Symposium on Molecular Spectroscopy, Columbus, Ohio, June 2013.
b
Li-Hong Xu, J. Fisher, R.M. Lees, H.Y. Shi, J.T. Hougen, J.C. Pearson, B.J. Drouin, G.A. Blake, R. Braakman, ”Torsion-Rotation Global Analysis of the First Three Torsional
States (vt = 0, 1, 2) and Terahertz Database for Methanol,” J. Mol. Spectrosc., 251, 305-313, (2008).
136
WG. Mini-symposium: Accelerator-Based Spectroscopy
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Chair: J. Oomens, Radboud University, Nijmegen, The Netherlands
WG01
INVITED TALK
1:30 – 2:00
IR SPECTROSCOPY ON PEPTIDES AND PROTEINS AFTER ION MOBILITY SELECTION AND IN LIQUID HELIUM
DROPLETS
GERT VON HELDEN, Department of Molecular Physics, Fritz-Haber-Institut der Max-Planck-Gesellschaft,
Berlin, Germany.
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IR spectroscopy has become a frequently used tool to characterize gas-phase peptides and proteins. In many experiments,
ions are m/z selected, irradiated by intense and tunable IR light and fragmentation is monitored as a function of IR wavelength.
The presence of different conformers can, however, complicate the interpretation, as the resulting spectra represent the sum
of the spectra of the individual components. We constructed a setup, in which ion mobility methods are used to obtain m/z
selected ions of defined shape on which are then further investigated by IR spectroscopy. First results on peptide aggregates
are presented and for some of those, the IR spectra show a transition from helical or random coil to beta sheet structures.
In a different experiment, peptide or protein ions are captures in liquid helium droplets prior to IR spectroscopic investigation.
The conditions inside a helium droplet are isothermal at 0.38 K and the interaction between the helium matrix and the
molecules are weak so that only small perturbations on the molecule are expected. IR spectra for m/z selected peptides with
up to 10 aminoacids and proteins containing more than 100 aminoacids have been measured. The spectra of the smaller
species show resolved bands of individual oscillators, which can be used for structure assignment. For the larger species,
band envelopes are obtained and for the case of highly charged proteins, a transition form helical to extended structures is
observed.
WG02
2:05 – 2:20
COMBINING THE POWER OF IRMPD WITH ION-MOLECULE REACTIONS: THE STRUCTURE AND REACTIVITY
OF RADICAL IONS OF CYSTEINE AND ITS DERIVATIVES
MICHAEL LESSLIE, Department of Chemistry and Biochemistry, Northern Illinois University, Dekalb, IL,
USA; SANDRA OSBURN, Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, PA,
USA; GIEL BERDEN, J. OOMENS, Institute for Molecules and Materials (IMM), Radboud University Nijmegen, Nijmegen, Netherlands; VICTOR RYZHOV, Department of Chemistry and Biochemistry, Northern Illinois University, Dekalb, IL, USA.
Most of the work on peptide radical cations has involved protons as the source of charge. Nonetheless, using metal ions
as charge sources often offers advantages like stabilization of the structure via multidentate coordination and the elimination
of the “mobile proton”. Moreover, characterization of metal-bound amino acids is of general interest as the interaction of
peptide side chains with metal ions in biological systems is known to occur extensively. In the current study, we generate
thiyl radicals of cysteine and homocysteine in the gas phase complexed to alkali metal ions. Subsequently, we utilize infrared
multiple-photon dissociation (IRMPD) and ion-molecule reactions (IMR) to characterize the structure and reactivity of these
radical ions.
Our group has worked extensively with the cysteine-based radical cations and anions, characterizing the gas-phase reactivity and rearrangement of the amino acid and several of its derivatives. In a continuation of this work, we are perusing the
effects of metal ions as the charge bearing species on the reactivity of the sulfur radical. Our S-nitroso chemistry can easily be
used in conjunction with metal ion coordination to produce initial S-based radicals in peptide radical-metal ion complexes. In
all cases we have been able to achieve radical formation with significant yield to study reactivity. Ion-molecule reactions of
metallated radicals with allyl iodide, dimethyl disulfide, and allyl bromide have all shown decreasing reactivity going down
group 1A.
Recently, we determined the experimental IR spectra for the homocysteine radical cation with Li+, Na+, and K+ as the
charge bearing species at the FELIX facility. For comparison, the protonated IR spectrum of homocysteine has previously
been obtained by our group. A preliminary match of the IR spectra has been confirmed. Finally, calculations are underway to
determine the bond distances of all the metal adduct structures.
137
WG03
2:22 – 2:37
FAR-IR ACTION SPECTROSCOPY OF AMINOPHENOL AND ETHYLVANILLIN: EXPERIMENT AND THEORY
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VASYL YATSYNA, RAIMUND FEIFEL, VITALI ZHAUNERCHYK, Department of Physics, Faculty of Science, University of Gothenburg, Gothenburg, Sweden; DANIËL BAKKER, ANOUK RIJS, FELIX Laboratory,
Radboud University Nijmegen, Nijmegen, The Netherlands.
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Investigations of molecular structure and conformational isomerism are at the forefront of today’s biophysics and biochemistry. In particular, vibrations excited by far-IR radiation can be highly sensitive to the molecular 3D structure as they
are delocalized over large parts of the molecule. Current theoretical predictions of vibrational frequencies in the far-IR range
are not accurate enough because of the non-local character and anharmonicity of these vibrations. Therefore experimental
studies in the far-IR are vital to guide theory towards improved methodology.
In this work we present the conformer-specific far-IR spectra of aminophenol and ethylvanillin molecules in the range
of 220-800 cm−1 utilizing ion-dip action spectroscopy carried out at the free electron laser FELIX in Nijmegen, Netherlands.
The systems studied are aromatic molecules with important functional groups such as the hydroxyl (OH) and amino (NH2 )
groups in aminophenol, and the hydroxyl, ethoxy (OCH2 CH3 ) and formyl (CHO) groups in ethylvanillin. The experimental
spectra show well resolved conformer-specific vibrational bands. In the case of ethylvanillin only two planar conformers have
been observed under supersonic jet expansion conditions. Despite the fact that these conformers differ only in the position of
oxygen of the formyl group with respect to ethoxy group, they are well distinguishable in far-IR spectra.
The capability of numerical methods based on density functional theory (DFT) for predicting vibrational frequencies
in this spectral region within the harmonic approximation has been investigated by using several hybrid-functionals such as
B3LYP, PBE0, B2PLYP and CAM-B3LYP. An anharmonic correction based on vibrational second order perturbation theory
approacha was also applied. We have found that the methods we considered are well suited for the assignment of far-IR
vibrational features except the modes which are strongly anharmonic, like the NH2 wagging mode in aminophenol which is
likely to be due to double well potential governing this motion.
a
V. Barone, Anharmonic vibrational properties by a fully automated second-order perturbative approach, J. Chem. Phys. 122 (2005) 014108.
WG04
2:39 – 2:54
OPPORTUNITIES FOR GAS-PHAS MOLECULAR SPECTROSCOPY ON THE VLS-PGM BEAMLINE AT THE CANADIAN LIGHT SOURCE
MICHAEL A MacDONALD, EFD, Canadian Light Source Inc., Saskatoon, Saskatchewan, Canada.
The VLS-PGM beamline at the Canadian Light Source cover the energy range from 12eV to 250eV with a resolving
power better than 104 throughout this range. Associated with this beamline are two endstations designed for gas phase
spectroscopy.
The first is a dual toroid electrostatic particle energy analyser. Each toroid can (independently) measure the energy
and angular distribution of charged particles emitted from the interaction region and can be set for either positive ions or
electrons. This allows both photoelectron and ion kinetic energy spectra to be recorded. Recent results from this instrument
will be presented including both high resolution photoelectron spectra and photoelectron asymmetry parameter (β) spectra.
Coincidence circuitry exists to allow, in favourable circumstances,the measurement of molecular frame photoelectron angular
distributions (MFPADs) where the detection of an ion fragment allows orientation of the parent molecule to be deduced.
The second is a Wiley-McLaren Time-of-Flight mass spectrometer equipped with multihit electronics. This allows
partial ion yield (PIY) spectra to be recorded as well as multi-ion coincidence spectra (PePIPICO). Again recent results will
be presented looking at double ionisation in benzene like molecules.
138
WG05
THERMAL DECOMPOSITION OF C7 H7 RADICALS; BENZYL, TROPYL, AND NORBORNADIENYL
2:56 – 3:11
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GRANT BUCKINGHAM, BARNEY ELLISON, JOHN W DAILY, Department of Chemistry and Biochemistry,
University of Colorado, Boulder, CO, USA; MUSAHID AHMED, UXSL, Chemical Sciences Division, Lawrence
Berkeley National Laboratory, Berkeley, CA, USA.
Benzyl radical (C6 H5 CH2 ) and two other C7 H7 radicals are commonly encountered in the combustion of substituted
aromatic compounds found in biofuels and gasoline. High temperature pyrolysis of benzyl radical requires isomerization to
other C7 H7 radicals that may include cycloheptatrienyl (tropyl) radical (cyc-C7 H7 ) and norbornadienyl radical. The thermal
decomposition of all three radicals has now been investigated using a micro-reactor that heats dilute gas-phase samples up to
1600 K and has a residence time of about 100 µ-sec. The pyrolysis products exit the reactor into a supersonic expansion and
are detected using synchrotron-based photoionization mass spectrometry and matrix-isolation IR spectroscopy. The products
of the pyrolysis of benzyl radical (C6 H5 CH2 ) along with three isotopomers (C6 H13
5 CH2 , C6 D5 CH2 , and C6 H5 CD2 ) were
detected and identifieda . The distribution of 13 C atoms and D atoms indicate that multiple different decomposition pathways
are active.
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a
Buckingham, G. T., Ormond, T. K., Porterfield, J. P., Hemberger, P., Kostko, O., Ahmed, M., Robichaud, D. J., Nimlos, M. R., Daily, J. W., Ellison, G. B. 2015, Journal of
Chemical Physics 142 044307
Intermission
WG06
NONDIPOLE EFFECTS IN CHIRAL SYSTEMS MEASURED WITH LINEARLY POLARIZED LIGHT
3:30 – 3:40
K P BOWEN, O HEMMERS, Chemistry, University of Nevada Las Vegas, Las Vegas, NV, USA; R GUILLEMIN,
Laboratoire de Chimie Physique – Matière et Rayonnement, Université Pierre et Marie Curie, Paris, France; W
C STOLTE, National Security Technologies, LLC, Livermore, CA, USA; M N PIANCASTELLI, Department of
Physics and Astronomy, Uppsala Universitet, Uppsala, Sweden; D W LINDLE, Chemistry, University of Nevada
Las Vegas, Las Vegas, NV, USA.
With the advent of third-generation synchrotron light sources, it has been demonstrated that higher-order corrections
to the dipole approximation are necessary for the description of light-matter interactions in the soft x-ray range. These
effects, known as ‘nondipole effects’, present themselves as asymmetries in the angular distributions of photoelectrons. Chiral
molecules, known to have asymmetries in photoelectron angular distributions when exposed to circularly polarized light, have
been proposed to demonstrate a chiral-specific nondipole effect when exposed to linearly polarized light. We present the firstever measurement of nondipole chiral angular distributions for the case of each enantiomer of camphor in the photon energy
range 296-343eV.
139
WG07
3:42 – 3:57
APPLICATIONS OF THE VUV FOURIER TRANSFORM SPECTROMETER AT SYNCHROTRON SOLEIL
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NELSON DE OLIVEIRA, DENIS JOYEUX, DESIRS Beamline, Synchrotron SOLEIL, Saint Aubin, France;
KENJI ITO, DESIRS beamline, Synchrotron Soleil, Saint-Aubin, France; BERENGER GANS, ISMO, CNRS,
Orsay, 91405, France; LAURENT NAHON, DESIRS Beamline, Synchrotron SOLEIL, Saint Aubin, France.
a
b
Nahon et al., J. Synchrotron Radiat., 19, 508(2012)
De Oliveira et al., Nat. Photonics, 5, 149(2011)
in
Fourier transform spectrometers (FTS) are usually based upon amplitude division interferometers through beamsplitters
(BS) as in the Michelson interferometer geometry. However, the manufacture of broadband BS is difficult and even impossible
in the far VUV (below λ = 140 nm). We therefore conceived an instrument based upon an original design involving only
reflective plane surfaces, giving access to the whole VUV range without the restrictions associated with BS. The VUV– FTS
is a permanent endstation connected to one of the three experimental branches of the DESIRS beamlinea and devoted to
high resolution photoabsorption in the UV-VUV spectral range, typically between λ = 300 and 40 nmb . Since 2008, a large
international community of users interested in laboratory measurements with applications in astrophysics, molecular physics
or planetary atmospheres has been attracted by the VUV - FTS capabilities including its efficiency in terms of signal to noise
ratio, even when high spectral resolution was not an issue. A large number of dedicated gas phase sample environments have
been developed including a windowless cell that can be cooled down, a heated windowless cell, a free molecular jet set-up
and various windowed cells. Besides, a new discharge gas cell for production and study of transient species gave recently
its first results. As an illustration, the VUV absorption spectrum of the CH3 radical down to 140 nm will be shown in this
presentation.
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WG08
FORBIDDEN TRANSITIONS IN THE VUV SPECTRUM OF N2
3:59 – 4:14
ALAN HEAYS, Leiden Observatory, University of Leiden, Leiden, Netherlands; MING LI NIU, LaserLaB Amsterdam, Vrije Universiteit Amsterdam, Amsterdam, Netherlands; NELSON DE OLIVEIRA, DESIRS Beamline,
Synchrotron SOLEIL, Saint Aubin, France; EDCEL JOHN SALUMBIDES, Department of Physics and Astronomy, VU University , Amsterdam, Netherlands; BRENTON R LEWIS, Research School of Physics and Engineering, Australian National University, Canberra, ACT, Australia; WIM UBACHS, Department of Physics and
Astronomy, VU University , Amsterdam, Netherlands; EWINE VAN DISHOECK, Leiden Observatory, University of Leiden, Leiden, Netherlands.
The predissociation of N2 excited levels is enabled by the presence of optically-inaccessible triplet states. We have
recorded vacuum ultraviolet (VUV) spectra at the SOLEIL synchrotron which reveal these states through their perturbation
of allowed transitions or their direct appearance due to intensity borrowing.
Some of these measurements were recorded at 900 K in order to access high-rotational levels, other measurements investigated weak forbidden transitions at high column density. Following careful analysis, significant new information has
been obtained elucidating the states responsible for the astrochemically and atmospherically signficant N2 predissociation
mechanism, and allowing for improvements in its quantitiative modelling.
WG09
SYNCHROTRON INFRARED SPECTROSCOPY OF ν4 , ν10 , ν11 AND ν14 STATES OF THIIRANE
4:16 – 4:31
COREY EVANS, JASON P CARTER, Department of Chemistry, University of Leicester, Leicester, United Kingdom; DON McNAUGHTON, ANDY WONG, School of Chemistry, Monash University, Melbourne, Victoria,
Australia; DOMINIQUE APPADOO, 800 Blackburn Road, Australian Synchrotron, Melbourne, Victoria, Australia.
The high-resolution (0.001 cm−1 ) spectrum of thiirane has been recorded using the infrared beamline at the Australian
synchrotron facility. Spectra have been recorded between 750 cm−1 to 1120 cm−1 and ro-vibrational transitions associated
with four bands have been observed and assigned. Coriolis coupling was observed between the ν4 (1024 cm−1 ) and the
ν14 (1050 cm−1 ) fundamentals as well as between ν11 (825 cm−1 ) and the ν8 (895 cm−1 ) fundamentals. The ν10 (945 cm−1 )
fundamental was also observed and was found to have no significant perturbations associated with it. For each of the observed
bands rotational, centrifugal distortion and Coriolis interaction parameters have been determined. The ground state constants
have also been further refined.
140
WG10
4:33 – 4:48
FINGERPRINTS OF INTRAMOLECULAR HYDROGEN BONDS: SYNCHROTRON-BASED FAR IR STUDY OF THE
CIS AND TRANS CONFORMERS OF 2-FLUOROPHENOL
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AIMEE BELL, JAMES SINGER, JENNIFER VAN WIJNGAARDEN, Department of Chemistry, University of
Manitoba, Winnipeg, MB, Canada.
Rotationally-resolved vibrational spectra of two planar conformers of 2-fluorophenol have been collected from 100-1000
cm−1 using the Bruker IFS125HR FTIR spectrometer at the Canadian Light Source with a resolution of 0.000959 cm−1 . The
cis conformer is lower in energy by 2.9 kcal/mol (MP2/aug-cc-pvDZ) and is thought to be stabilized by an intramolecular
hydrogen bond between the hydroxyl group and neighbouring fluorine atom on the ring. The OH out-of-plane torsion bands
below 400 cm−1 provide the best fingerprint to distinguish between the two conformers in the gas phase spectrum as the c-type
band origin of the cis conformer is blue-shifted by 36 cm−1 from that of the trans conformer as result of the intramolecular
interaction. In this talk, we will discuss the progress of the analysis of this complex far infrared spectrum of 2-fluorophenol.
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WG11
4:50 – 5:05
INFRARED CROSS-SECTIONS OF NITRO-DERIVATIVE VAPORS: NEW SPECTROSCOPIC SIGNATURES OF EXPLOSIVE TAGGANTS AND DEGRADATION PRODUCTS
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ARNAUD CUISSET, GAËL MOURET, Laboratoire de Physico-Chimie de l’Atmosphère, Université du Littoral
Côte d’Opale, Dunkerque, France; OLIVIER PIRALI, SÉBASTIEN GRUET, AILES beamline, Synchrotron
SOLEIL, Saint Aubin, France; GÉRARD PASCAL PIAU, GILLES FOURNIER, Airbus Group Innovations,
Airbus, Suresnes, France.
Classical explosives such as RDX or TNT exhibit a very low vapor pressure at room temperature and their detection in air
requires very sensitive techniques with levels usually better than 1 ppb. To overcome this difficulty, it is not the explosive itself
which is detected, but another compound more volatile present in the explosive. a This volatile compound can exist naturally
in the explosive due to the manufacturing process. For example, in the case of DiNitroToluene (DNT), the molecule is a
degradation product of TNT and is required for its manufacture. Ortho-Mononitrotoluene (2-NT) and para-mononitrotoluene
(4-NT) can be also used as detection taggants for explosive detection.
In this study, using the exceptional properties of the SOLEIL synchrotron source, and adapted multipass-cells, gas phase
Far-IR rovibrational spectra of different isomers of mononitrotoluene and dinitrotoluene have been investigated. Room temperature Far-IR cross-sections of the 3 isomer forms of mononitrotoluene have been determined for the lowest frequency
vibrational bands located below 700 cm−1 .b Cross sections and their temperature dependences have been also measured in
the Mid-IR using conventional FTIR spectroscopy probing the nitro-derivatives vapors in a heated multipass-cell.
a
b
J. C. Oxley, J. L. Smith, W. Luo, J. Brady, Prop. Explos. Pyrotec. 34 (2009) 539–543
A. Cuisset, S. Gruet, O. Pirali, G. Mouret, Spectrochimica Acta Part A, 132 (2014) 838-845.
WG12
5:07 – 5:22
CHARACTERIZATION OF REACTION PATHWAYS IN LOW TEMPERATURE OXIDATION OF TETRAHYDROFURAN WITH MULTIPLEXED PHOTOIONIZATION MASS SPECTROMETRY TECHNIQUE
IVAN ANTONOV, LEONID SHEPS, Combustion Research Facility, Sandia National Laboratories, Livermore,
CA, USA.
Tetrahydrofuran (THF) is a prototype biofuel and a common intermediate in combustion of alkanes and alkenes. Photolytic Cl atom-initiated oxidation of THF was studied with multiplexed photoionization mass spectrometry (MPIMS) technique at temperatures 400-650 K and pressures 0.005-2 bar. Photoionization spectra and kinetic time traces were recorded simultaneously for all mass channels. Photoionization spectra, recorded with tunable VUV synchrotron radiation, were used to
separate and identify isomers with the same nominal molecular formula, providing mechanistic insight into the the underlying
kinetics. Our study suggests that formation of alkylperoxy radicals and their subsequent isomerization to hydroperoxyalkyl
radicals plays an important role in low temperature oxidation of THF, while ring opening of THF−H radical (which dominates
THF oxidation at T>800 K) is less important at our conditions.
141
WH. Clusters/Complexes
Chair: Elangannan Arunan, Indian Institute of Science, Bangalore, India
1:30 – 1:45
ar
y
WH01
A STRANGE COMBINATION BAND OF THE CROSS-SHAPED COMPLEX CO2 -CS2
NASSER MOAZZEN-AHMADI, Department of Physics and Astronomy, University of Calgary, Calgary, AB,
Canada; BOB McKELLAR, Steacie Laboratory, National Research Council of Canada, Ottawa, ON, Canada.
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The spectrum of the weakly-bound CO2 -CS2 complex was originally studied by the USC group,a using a pulsed supersonic expansion and a tunable diode laser in the CO2 ν3 region. Their derived structure was nonplanar X-shaped (C2v
symmetry), a relatively unusual geometry among linear molecule dimers. Very recently, there has been a detailed theoretical
study of this complex based on a high-level ab initio potential surface.b The theoretical ground state is X-shaped, in good
agreement with experiment, and a very low-lying (3 cm−1 at equilibrium, or 8 cm−1 zero-point) slipped-parallel isomer is
also found.
We report here two new combination bands of X-shaped CO2 -CS2 which involve the same ν3 fundamental (2346.546
cm−1 ) plus a low-frequency intermolecular vibration. The first band has b-type rotational selection rules (the fundamental
is c-type). This, and its location (2361.838 cm−1 ), clearly identify it as being due to the intermolecular torsional mode.
The second band (2388.426 cm−1 ) is a-type and can be assigned to the CO2 rocking mode. Both observed intermolecular
frequencies (15.29 and 41.88 cm−1 ) are in extremely good agreement with theory (15.26 and 41.92 cm−1 ).b The torsional
band is well-behaved, but the 2388 cm−1 band is bizarre, with its Ka = 2 ← 2 and 4 ← 4 components displaced upward by
2.03 and 2.62 cm−1 relative to the Ka = 0 ← 0 origin (odd Ka values are nuclear spin forbidden). A qualitatively similar
shift (+2.4 cm−1 ) was noted for the (forbidden) Ka = 1 level of this mode by Brown et al.,b but the calculation was limited to
J = 0 and 1. These huge shifts are presumably due to hindered internal rotation effects.
a
b
C.C. Dutton, D.A. Dows, R. Eikey. S. Evans, R.A. Beaudet, J. Phys. Chem. A 102, 6904 (1998).
J. Brown, X.-G. Wang, T. Carrington, Jr., G.S. Grubbs II, and R. Dawes, J. Chem. Phys. 140, 114303 (2014).
WH02
1:47 – 2:02
RE-ANALYSIS OF THE DISPERSED FLUORESCENCE SPECTRA OF THE C3 -RARE GAS ATOM COMPLEXES
YI-JEN WANG, Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei, Taiwan; ANTHONY
MERER, Department of Chemistry, University of British Columbia, Vancouver, BC, Canada; YEN-CHU HSU,
Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei, Taiwan.
The dispersed fluorescence (DF) spectra of the C3 Ne, C3 Ar, C3 Kr, and C3 Xe complexes near the 0 2− 0- 000, 0 4− 0000, 0 2+ 0- 000 and 100-000 bands of the Ã-X̃ system of C3 a have been revisited. Some of the DF spectra of the Ne and
Ar complexes have been recently obtained with a slightly improved resolution of 6-10 cm−1 . All the DF spectra have been
reassigned as emission from van der Waals (vdW) complexes and C3 fragments. The optically excited C3 -Rg (Rg = rare-gas
atom) complexes fluorescence and/or decay down to slightly lower (about 2-30 cm−1 ) vibrational levels without changing the
internal energy of C3 and then predissociate via the continua of the nearby vibronic states of C3 . The available dissociation
channels depend on the binding energy of the ground electronic state complex. Exceptions have been found at the vdW
bands near the 0 4− 0- 000 band of C3 . The binding energies of the ground electronic states of these four complexes will be
discussed.
a
G. Zhang, B.-G. Lin, S.-M. Wen, and Y.-C. Hsu, J. Chem. Phys. 120, 3189(2004); J.-M. Chao, K. S. Tham, G. Zhang, A. J. Merer, Y.-C. Hsu, and W.-P. Hu, J. Chem. Phys.
134, 074313(2011)
WH03
2:04 – 2:19
INFARED SPECTROSCOPY OF Mn(CO2 )−
n CLUSTER ANIONS
MICHAEL C THOMPSON, J. MATHIAS WEBER, JILA and the Department of Chemistry and Biochemistry,
University of Colorado-Boulder, Boulder, CO, USA.
We present infrared photodissociation spectra of Mn(CO2 )−
n (n = 2 − 10) cluster ions. The spectra are interpreted in
the framework of density functional theory and compared to other first-row transition metals in anionic clusters with CO2 ,
allowing to draw conclusions to the structure and spin state of the charge carrier.
142
WH04
INFRARED SPECTROSCOPY OF
2:21 – 2:36
(N2 O)−
n
−
AND (N2 O)m O CLUSTER ANIONS
MICHAEL C THOMPSON, J. MATHIAS WEBER, JILA and the Department of Chemistry and Biochemistry,
University of Colorado-Boulder, Boulder, CO, USA.
ar
y
−
We report infrared photodissociation spectra of nitrous oxide cluster anions, (N2 O)−
n (n = 7 − 11) and (N2 O)m O
(m = 1 − 13). Structural changes of the charge carrier in the clusters are driven by increasing levels of solvation. The spectra
are interpreted by comparison with quantum chemical calculations.
WH05
2:38 – 2:53
+
INFRARED SPECTROSCOPY OF PHENOL -TRIETHYLSILANE DIHYDROGEN-BONDED CLUSTER: INTRINSIC
STRENGTH OF THE Si-H· · · H-O DYHYDROGEN BOND
in
HARUKI ISHIKAWA, TAKAYUKI KAWASAKI, RISA INOMATA, Department of Chemistry, School of Science, Kitasato University, Sagamihara, Japan.
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Dihydrogen bond is known to be one of the unconventional hydrogen bonds. When a hydrogen atom is bonded to an
electropositive atom, such as B, Al, and so on, the hydrogen atom has a partial negative charge. Then, a hydrogen-bond
type interaction are formed between the oppositely charged two hydrogen atoms. This interaction is called a dihydrogen
bond. In the previous study, we reported the infrared spectroscopy of neutral phenol (PhOH)-triethylsilane (TES) clustera .
It was suggested that the Si-H· · · H-O dihydrogen bond should be as strong as the π-type hydrogen bond. In the present
study, to investigate the intrinsic strength of the Si-H· · · H-O dihydrogen bond, infrared photodissociation spectroscopy on
the PhOH+ -TES and PhOH+ -diethylmethysilane (DEMS) cationic clusteris was carried outb .
Both of the clusters exhibit a very broad and intense band centered at about 2860 cm−1 . This band is assigned as the OH
stretching band of the PhOH+ moiety. Based on the amount of the red-shift of the OH stretching band and the results of the
theoretical calculations, the intrinsic strength of the Si-H· · · H-O dihydrogen bond is evaluated to be stronger than that of the
π-type hydrogen bond. The proton affinities of TES and DEMS estimated by the theoretical calculation are larger than those
of benzene and ethylene. These results are consistent with our experimental observations.
a
b
H. Ishikawa, T. Kawasaki, RJ02, the 68th International Symposium on Molecular Spectroscopy (2013)
H. Ishikawa, T. Kawasaki, R. Inomata, J. Phys. Chem. A 119, 601 (2015).
WH06
INFRARED SPECTROSCOPY OF HYDROGEN-BONDED CLUSTERS OF PROTONATED HISTIDINE
2:55 – 3:10
MAKOTO KONDO, YASUTOSHI KASAHARA, HARUKI ISHIKAWA, Department of Chemistry, School of
Science, Kitasato University, Sagamihara, Japan.
Histidine(His), one of the essential amino acids, is involved in active sites in many enzyme proteins, and known to play
fundamental roles in human body. Thus, to gain detailed information about intermolecular interactions of His as well as its
structure is very important. In the present study, we have recorded IR spectra of hydrogen-bonded clusters of protonated His
(HisH+ ) in the gas phase to discuss the relation between the molecular structure and intermolecular interaction of HisH+ .
Clusters of HisH+ -(MeOH)n (n = 1, 2) were generated by an electrospray ionization of the MeOH solution of L-His hydrochloride monohydrate. IR photodissociation spectra of HisH+ -(MeOH)1,2 were recorded. By comparing with the results
of the DFT calculations, we determined the structures of these clusters. In the case of n = 1 cluster, MeOH is bonded to the
imidazole ring as a proton acceptor. The most of vibrational bands observed were well explained by this isomer. However,
a free NH stretch band of the imidazole ring was also observed in the spectrum. This indicates an existence of an isomer in
which MeOH is bounded to the carboxyl group of HisH+ . Furthermore, it is found that a protonated position of His is influenced by a hydrogen bonding position of MeOH. In the case of n = 2 cluster, one MeOH molecule is bonded to the amino
group, while the other MeOH molecule is separately bonded to the carboxyl group in the most stable isomer. However, there
is a possibility that other conformers also exist in our experimental condition. The details of the experimental and theoretical
results will be presented in the paper.
143
WH07
3:12 – 3:27
−
THEORETICAL INVESTIGATION OF THE UV/VIS PHOTODISSOCIATION DYNAMICS OF ICN (Ar)n and
BrCN− (Ar)n
ar
y
BERNICE OPOKU-AGYEMAN, ANNE B McCOY, Department of Chemistry and Biochemistry, The Ohio State
University, Columbus, OH, USA.
a
in
An interesting experimental observation in the photodissociation dynamics of ICN– (Ar)n is that, even in Ar–ICN– , a
small fraction of the products recombine to form ICN– following electronic excitation.a The two electronic states that are
experimentally accessible dissociate into X∗ + CN– and X– + CN (X=I or Br). The energy differences between these two
asymptotes are roughly 0.14 eV and -0.04 eV for ICN– and BrCN– , respectively.a,b The addition of an argon atom is expected
to shift the relative energies of these potential energy surfaces, and provide a mechanism for dissipating some of the excess
energy from the electronically excited ICN– and BrCN– , altering the product branching.
In this study, the effects of argon solvation are investigated using classical dynamics approaches. In order to simulate the
dynamics, potential energy surfaces for the argon clusters are developed using the results obtained from electronic structure
calculations of the fragments in the clusters. Specifically, the potential energies are approximated as the interaction in the bare
anion and pair-wise interactions between the argon and the dissociation products. The dynamics are then carried out using
classical mechanics. Non-adiabatic effects are treated by incorporating surface hopping into the dynamics.c To assess the
accuracy of the approach, the branching ratios for the bare anions are calculated using classical dynamics and the results are
then compared to the previously reported quantum dynamics results.a,b Once the results from both the quantum and classical
dynamics are shown to be consistent, classical dynamics simulations are then carried out on the clusters.
A. S. Case, E. M. Miller, J. P. Martin, Y. J. Lu, L. Sheps, A. B. McCoy, and W. C. Lineberger, Angew. Chem., Int. Ed. 51, 2651 (2012).
B. Opoku-Agyeman, A. S. Case, J. H. Lehman, W. Carl Lineberger and A. B. McCoy, J. Chem Phys. 141, 084305 (2014).
c
J. C. Tully, J. Chem Phys. 93, 1061 (1990).
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b
WH08
3:29 – 3:44
DISPERSION-DOMINATED π -STACKED COMPLEXES CONSTRUCTED ON A DYNAMIC SCAFFOLD
DEACON NEMCHICK, MICHAEL COHEN, PATRICK VACCARO, Department of Chemistry, Yale University,
New Haven, CT, USA.
The non-covalent interactions responsible for π-stacking play crucial roles in many fields of modern chemistry, influencing topics ranging from assembly and recognition in biomolecular systems to the design and function of nano-materials.
Owing to the propensity for stronger non-aryl forces (e.g., hydrogen bonding) to dominate complex formation, the number
of detailed laser-spectroscopic studies on π-bound species is surprisingly limited, with most reported examples focusing on
adducts involving combinations of benzene (Bz) and/or substituted-benzene derivatives. A concerted experimental and theoretical effort has been undertaken to explore novel π-stacking motifs based on the non-benzoidal framework of tropolone
(TrOH), where the potentially frustrated (tunneling-mediated) transfer of a proton between donor and acceptor sites can afford an in situ probe of non-covalent binding. Laser-induced fluorescence spectra acquired for the binary TrOH·Bz complex
synthesized under cryogenic free-jet expansion conditions show extensive vibronic features that are red-shifted from the intense Ã1 B2 −X̃1 A1 absorption resonance of the bare TrOH substrate and display intensity patterns indicative of changing
intermolecular potential-surface topography upon π ∗ ← π electron promotion. These results, as well as spectral signatures
from intramolecular TrOH reaction dynamics, will be discussed, with complimentary quantum-chemical calculations serving
to provide new insights into the nature of weak, dispersion-dominated interactions.
Intermission
144
WH09
4:03 – 4:18
THE COMPETITION BETWEEN INSERTION AND SURFACE BINDING OF BENZENE TO THE WATER HEPTAMER
ar
y
PATRICK S. WALSH, Department of Chemistry, Purdue University, West Lafayette, IN, USA; DANIEL P. TABOR, EDWIN SIBERT, Department of Chemistry, The Univeristy of Wisconsin, Madison, WI, USA; TIMOTHY
S. ZWIER, Department of Chemistry, Purdue University, West Lafayette, IN, USA.
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Previous work on the benzene-(water)n clusters with n=7 have focused attention on the main conformer, whose S0 -S1
61 0 R2PI transition appears +138 cm−1 above the benzene monomer. Using resonant ion-dip infrared spectroscopy with a
higher resolution IR source, we have recently returned to this cluster to record improved OH stretch infrared spectra and
more thoroughly consider the possible Bz-(H2 O)7 structures that might give rise to it. Analysis of that spectrum led to its
assignment as an inserted cube structure with pseudo-S4 symmetry. This talk will consider the spectrum and structure of a
minor conformer of Bz-(H2 O)7 with R2PI transition 65 cm−1 to the blue of the monomer. This spectrum, recorded for the
first time, shows a distinctive OH stretch infrared spectrum that is best matched with an expanded prism structure in which
the seventh water molecule inserts into one edge of the hexamer prism. In this case, benzene acts as acceptor for an OH... π Hbond, sitting on the surface of a preformed water heptamer structure. The infrared spectra of the two Bz-(H2 O)7 structures are
compared, and the results of a local mode Hamiltonian model are applied to make an assignment for the observed structure.
The monomer Hamiltonians resulting from this model shed light on the unique two- and three-coordinate water molecules
found in this structure.
WH10
VIBRATIONAL SPECTROSCOPY OF BENZENE-(WATER)N CLUSTERS WITH N = 6, 7
4:20 – 4:35
DANIEL P. TABOR, EDWIN SIBERT, Department of Chemistry, The Univeristy of Wisconsin, Madison, WI,
USA; RYOJI KUSAKA, Chemistry, Hiroshima University, Higashi-Hiroshima, Japan; PATRICK S. WALSH,
TIMOTHY S. ZWIER, Department of Chemistry, Purdue University, West Lafayette, IN, USA.
The investigation of benzene-water clusters (Bz-(H2 O)n ) provides insight into the relative importance π-hydrogen bond
interactions in cluster formation. Taking advantage of the higher resolution of current IR sources, isomer-specific resonant
ion-dip infrared (RIDIR) spectra were recorded in the OH stretch region (3000-3750 cm−1 ). A local mode Hamiltonian
for describing the OH stretch vibrations of water clusters is applied to Bz-(H2 O)6 and Bz-(H2 O)7 and compared with the
RIDIR spectra. These clusters are the smallest water clusters in which three-dimensional H-bonded networks containing
three-coordinate water molecules begin to be formed, and are therefore particularly susceptible to re-ordering or re-shaping in
response to the presence of a benzene molecule. The spectrum of Bz-(H2 O)6 is assigned to an inverted book structure while
the major conformer of Bz-(H2 O)7 is assigned to an S4 -derived inserted cubic structure in which the benzene occupies one
corner of the cube. The local mode model is used to extract monomer Hamiltonians for individual water molecules, including
stretch-bend Fermi resonance and intra-monomer couplings. The monomer Hamiltonians divide into sub-groups based on
their local H-bonding architecture (DA, DDA, DAA) and the nature of their interaction with benzene.
145
WH11
THEORETICAL STUDY OF THE IR SPECTROSCOPY OF BENZENE-(WATER)N CLUSTERS
4:37 – 4:52
ar
y
DANIEL P. TABOR, EDWIN SIBERT, Department of Chemistry, The Univeristy of Wisconsin, Madison, WI,
USA; RYOJI KUSAKA, Chemistry, Hiroshima University, Higashi-Hiroshima, Japan; PATRICK S. WALSH,
TIMOTHY S. ZWIER, Department of Chemistry, Purdue University, West Lafayette, IN, USA.
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The local mode Hamiltonian that assigns RIDIR spectra for Bz-(H2 O)6 and Bz-(H2 O)7 is explored in detail for Bz(H2 O)n with n = 3 − 7. In addition to contributions from OH stretches, the Hamiltonian includes the anharmonic coupling
of each water monomer’s bend overtone and its OH stretch fundamentals, which is necessary for accurately modeling 31503300 cm−1 region of the spectra. The parameters of the Hamiltonian can be calculated using either MP2 or density functional
theory. The relative strengths and weaknesses of these two electronic structure approaches are examined to gain further
physical understanding. Initial assignments of Bz-(H2 O)6 and Bz-(H2 O)7 were based on a linear scaling of M06-2X harmonic
frequencies. In most cases, counterpoise-corrected MP2 calculations obtain similar frequencies (across all cluster sizes) if
stretch anharmonicity is taken into account. Individual “monomer Hamiltonians” are constructed via the application of fourth
order Van Vleck perturbation theory to MP2 potential energy surfaces. These calculations elucidate the sensitivity of intramonomer couplings to chemical environment. The presence of benzene has particularly important consequences for the
spectra of the Bz-(H2 O)3−5 clusters, in which the symmetry of the water cycles is broken by π-H-bonding to benzene. The
nature of these perturbations is discussed.
WH12
4:54 – 5:09
SPECTROSCOPIC INVESTIGATION OF TEMPERATURE EFFECTS ON THE HYDRATION STRUCTURE OF THE
PHENOL CLUSTER CATION
REONA YAGI, YASUTOSHI KASAHARA, HARUKI ISHIKAWA, Department of Chemistry, School of Science, Kitasato University, Sagamihara, Japan.
Owing to recent technical developments of various spectroscopies, microscopic hydration structures of various clusters
in the gas phase have been determined so far. The next step for further understanding of the microscopic hydration is to
reveal the temperature effect, such as a fluctuation of the hydration structure. Thus, we are carrying out photodissociation
spectroscopy on the hydrated phenol cation clusters, [PhOH(H2 O)n ]+ . Since electronic spectra of [PhOH(H2 O)n ]+ have
been reported alreadya , this system is suitable for our purpose.
In the present study, we use our temperature-variable 22-pole ion trap apparatusb . The ions in the trap become thermal
equilibrium condition by multiple collisions with temperature-controlled He buffer gas. By this way, the temperature of the
ions can be controlled.
In the electronic spectrum of the n = 5 cluster measured at 30 K, a sharp band is observed. It shows that the temperature
of ions are well-controlled. Contrary to the n = 5 cluster, the n = 6 cluster exhibits a wider band shape. The temperature
dependence of the band shape indicates the existence of several, at least two, isomers in the present experimental condition.
a
b
S. Sato, N. Mikami J. Phys. Chem. 100, 4765 (1996).
H. Ishikawa, T. Nakano, T. Eguchi, T. Shibukawa, K. Fuke Chem. Phys. Lett. 514, 234 (2011).
146
WH13
5:11 – 5:26
ULTRAVIORET AND INFRARED PHOTODISSOCIATION SPECTROSCOPY OF HYDRATED ANILINIUM ION
ITARU KURUSU, REONA YAGI, YASUTOSHI KASAHARA, HARUKI ISHIKAWA, Department of Chemistry, School of Science, Kitasato University, Sagamihara, Japan.
a
b
R. Yagi, Y. Kasahara, H. Ishikawa, the 70th International Symposium on Molecular Spectroscopy (2015).
H. Ishikawa, T. Nakano, T. Eguchi, T. Shibukawa, K. Fuke Chem. Phys. Lett. 514, 234 (2011).
G. Féraud, et al. Phys. Chem. Chem. Phys. 16, 5250 (2014).
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To understand the temperature effect on the microscopic hydration, we have been carrying out the laser spectroscopy of
temperature-controlled hydrated phenol cation clusters using our temperature-variable ion trap apparatusa,b . In the present
study, we have chosen an anilinium ion (AnH+ ) as a solute. Since the phenol cation has (π)−1 configuration, the phenyl ring
does not play as a proton-acceptor. On the contrary, the π-orbitals in the AnH+ are fulfilled and both the NH+
3 and phenyl
groups can behave as hydrogen-bonding sites. Thus, hydration structures around the AnH+ are expected to be different from
those of the phenol cation. Since there is no spectroscopic report on the hydrated AnH+ clusters, we have carried out the UV
and IR photodissociation spectroscopy of AnH+ (H2 O) clusters.
In the present study, the AnH+ (H2 O) is produced by an electrospray ionization method. As the first step, spectroscopic
measurements are carried out without temperature control. In the UV photodissociation spectrum, the 0-0 band appears
at 36351 cm−1 which is red-shifted by 1863 cm−1 from that of the AnH+ monomerc . The band pattern is similar to that
of the AnH+ monomer. This indicates that the structure of the AnH+ is not so affected by the single hydration. In the
IR photodissociation spectrum, OH stretching band of the H2 O moiety and free NH stretching band of AnH+ moiety are
observed. Comparison with the results of the DFT calculation at M05-2X/6-31++G(d,p) level, we determined the structure of
the AnH+ (H2 O) cluster.
WH14
5:28 – 5:43
WATER-NETWORK MEDIATED, ELECTRON INDUCED PROTON TRANSFER IN ANIONIC [C5 H5 N·(H2 O)n ]−
CLUSTERS: SIZE DEPENDENT FORMATION OF THE PYRIDINIUM RADICAL FOR n ≥ 3
ANDREW F DeBLASE, Department of Chemistry, Purdue University, West Lafayette, IN, USA; GARY H WEDDLE, Department of Chemistry and Biochemistry, Fairfield University, Fairfield, CT, USA; KAYE A ARCHER,
KENNETH D. JORDAN, Department of Chemistry, University of Pittsburgh, Pittsburgh, PA, USA; MARK
JOHNSON, Department of Chemistry, Yale University, New Haven, CT, USA.
As an isolated species, the radical anion of pyridine (Py− ) exists as an unstable transient negative ion, while in aqueous
environments it is known to undergo rapid protonation to form the neutral pyridinium radical [PyH(0) ] along with hydroxide.
Furthermore, the negative adiabatic electron affinity (AEA) of Py− can become diminished by the solvation energy associated
with cluster formation. In this work, we focus on the hydrates [Py·(H2 O) n]− with n = 3-5 and elucidate the structures of
these water clusters using a combination of vibrational predissociation and photoelectron spectroscopies. We show that Htrasfer to form PyH(0) occurs in these clusters by the infrared signature of the nascent hydroxide ion and by the sharp bending
vibrations of aromatic ring CH bending.
147
WI. Astronomy
ar
y
Chair: Holger S. P. Müller, Universität zu Köln, Köln, NRW, Germany
WI01
1:30 – 1:45
THE NEW ALMA PROTOTYPE 12 M TELSCOPE OF THE ARIZONA RADIO OBSERVATORY: TRANSPORT,
RECOMMISSIONING, AND FIRST LIGHT
LUCY ZIURYS, Department of Chemistry and Biochemistry, University of Arizona, Tucson, AZ, USA; N J
EMERSON, T W FOLKERS, R W FREUND, D FORBES, G P REILAND, M McCOLL, S C KEEL, S
H WARNER, J KINGSLEY, Steward Observatory, University of Arizona, Tucson, AZ, USA; DeWAYNE T
HALFEN, Department of Chemistry and Astronomy, University of Arizona, Tucson, AZ, USA.
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In March 2013, the Arizona Radio Observatory (ARO) acquired the European 12 m prototype antenna of the Atacama
Large Millimeter Array (ALMA) from the European Southern Observatory (ESO). The antenna was located at the Very Large
Array (VLA) site near Socorro, New Mexico. During the summer of 2013, the antenna was prepared for the move to the
ARO Kitt Peak site in Arizona, and in November 2013, the actual transport began. The 97 ton antenna was transported to
Arizona in two major parts: the 40 ft. reflector and the base/receiver cabin, which were reassembled in the dome at Kitt Peak
in December 2013. Recommissioning began in January 2014, and “first light” observations occurred in September 2014 at
115 GHz. Scientific observations began in December 2014.
WI02
1:47 – 2:02
FIRST SCIENTIFIC OBSERVATIONS WITH THE NEW ALMA PROTOTYPE ANTENNA OF THE ARIZONA RADIO
OBSERVATORY: HCN AND CCH IN THE HELIX NEBULA
LUCY ZIURYS, Department of Chemistry and Biochemistry, University of Arizona, Tucson, AZ, USA; DEBORAH SCHMIDT, Department of Astronomy, University of Arizona, Tucson, AZ, USA.
Observations have been conducted with the new 12 m antenna of the Arizona Radio Observatory (ARO) at 3 mm towards
the Helix Nebula. This object is the oldest known planetary nebula. The J = 1 → 0 transition of HCN at 88 GHz and two
hyperfine components of the N = 1 → 0 line of CCH at 87 GHz were observed towards nine positions sampling different
regions across the nebula. Both molecules were detected at all positions at the 5 – 30 mK intensity level. The line profiles
exhibited multiple velocity components, as also seen in HCO+ and H2 CO towards the same positions. The widespread
distribution of HCN and CCH at this late stage of stellar evolution is further evidence that polyatomic molecules are being
dispersed into the ISM. It also suggests that the progenitor star in the Helix is carbon-rich.
WI03
CCH AND HNC IN PLANETARY NEBULAE
2:04 – 2:19
DEBORAH SCHMIDT, Department of Astronomy, University of Arizona, Tucson, AZ, USA; LUCY ZIURYS,
Department of Chemistry and Biochemistry, University of Arizona, Tucson, AZ, USA.
A survey of CCH and HNC has been conducted towards a sample of ten planetary nebulae of varying ages using the
Submillimeter Telescope (SMT) of the Arizona Radio Observatory (ARO) at 1 mm. The N = 3 → 2 transition of CCH at
262 GHz and the J = 3 → 2 line of HNC at 272 GHz were observed using the ALMA Band 6 receiver at the SMT. The
molecules were detected in most of the sources where HCN and HCO+ had been identified in a previous survey. Molecular
abundances for CCH and HNC have been determined in these nebulae, as well as [HCN]/[HNC] ratios. These observations
further support the notion that the chemistry in planetary nebulae remains active despite the ultraviolet radiation field from
the central white dwarf star.
148
WI04
MAPPING THE SPATIAL DISTRIBUTION OF METAL-BEARING OXIDES IN VY CANIS MAJORIS
2:21 – 2:36
ar
y
ANDREW BURKHARDT, S. TOM BOOTH, Department of Astronomy, The University of Virginia, Charlottesville, VA, USA; ANTHONY REMIJAN, ALMA, National Radio Astronomy Observatory, Charlottesville,
VA, USA; BRANDON CARROLL, Division of Chemistry and Chemical Engineering, California Institute of
Technology, Pasadena, CA, USA; LUCY ZIURYS, Department of Astronomy, University of Arizona, Tucson, AZ,
USA.
in
The formation of silicate-based dust grains is not well constrained. Despite this, grain surface chemistry is essential to
modern astrochemical formation models. In carbon-poor stellar envelopes, such as the red hypergiant VY Canis Majoris (VY
CMa), metal-bearing oxides, the building blocks of silicate grains, dominate the grain formation, and thus are a key location
to study dust chemistry. TiO2 , which was only first detected in the radio recently (Kaminski et al., 2013a), has been proposed
to be a critical molecule for silicate grain formation, and not oxides containing more abundant metals (eg. Si, Fe, and Mg)
(Gail and Sedlmayr, 1998). In addition, other molecules, such as SO2 , have been found to trace shells produced by numerous
outflows pushing through the expanding envelope, resulting in a complex velocity structure (Ziurys et al., 2007). With the
advanced capabilities of ALMA, it is now possible to individually resolve the velocity structure of each of these outflows and
constrain the underlying chemistry in the region. Here, we present high resolution maps of rotational transitions of several
metal-bearing oxides in VY CMa from the ALMA Band 7 and Band 9 Science Verification observations. With these maps,
the physical parameters of the region and the formation chemistry of metal-bearing oxides will be studied.
WI05
+
2:38 – 2:53
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C AND THE CONNECTION BETWEEN DIFFERENT TRACERS OF THE DIFFUSE INTERSTELLAR MEDIUM
STEVEN FEDERMAN, JOHNATHAN S RICE, Physics and Astronomy, University of Toledo, Toledo, OH, USA;
JORGE L PINEDA, WILLIAM D LANGER, PAUL F GOLDSMITH, Jet Propulsion Laboratory, California
Institute of Technology, Pasadena, CA, USA; NICOLAS FLAGEY, Institute for Astronomy, University of Hawaii,
Hilo, Hawaii, USA.
Using radio, microwave, sub-mm, and optical data, we analyze several lines of sight toward stars generally closer than 1
kpc on a component by component basis. We derive the component structure seen in emission from C+ , H I, and CO and its
isotopoloques, along with those for CH+ , CH, CN, Ca II, and Ca I in absorption. We study how these tracers are related to the
CO-Dark H2 gas being probed by C+ emission and discuss the kinematic connections among the species. Physical conditions
of the various components seen in absorption, especially density, are inferred from a simple chemical analysis based on the
column densities of CH+ , CH, and CN.
WI06
2:55 – 3:10
INFERRING THE TEMPERATURE AND DENSITY OF DIFFUSE INTERSTELLAR CLOUDS FROM C3 OBSERVATIONS
NICOLE KOEPPEN, Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL,
USA; BENJAMIN J. McCALL, Departments of Chemistry and Astronomy, University of Illinois at UrbanaChampaign, Urbana, IL, USA.
Observations of carbon chain molecules are useful in determining the number densities and temperatures of diffuse
interstellar clouds. In 2003, C3 was observed towards ten different sightlines and the rotational distributions were determined
using the oscillator strengths available at that time.a The population of each rotational level was adjusted individually in
order to obtain the best fit for all of the P, Q, and R branch lines. This past year, the effect of perturbing states on the C3
spectrum was elucidated, and improved oscillator strengths determined.b With these new values, we have redetermined the
rotational distribution of C3 in these ten sightlines, and used a rotational excitation model analogous to that of Roueff et al.c
and collisional cross sections from Smith et al.d to infer the kinetic temperatures and number densities.
a
Adamkovics et al. Ap.J., 595, 235 (2003)
Schmidt et al. MNRAS, 441, 1134 (2014)
c
Roueff et al. A&A, 384, 629 (2002)
d
Smith et al. J. Phys. Chem. A, 118, 6351 (2014)
b
149
WI07
3:12 – 3:27
NEW BACKGROUND INFRARED SOURCES FOR STUDYING THE GALACTIC CENTER’S INTERSTELLAR GAS
ar
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THOMAS R. GEBALLE, Gemini Observatory, Hilo, HI, USA; TAKESHI OKA, Department of Astronomy and
Astrophysics, Chemistry, The University of Chicago, Chicago, IL, USA; E. LAMBRIDES, Astrophysics, American Museum of Natural History, New York, NY, USA; S. C. C. YEH, , Subaru Telescope, Hilo, HI, USA; B.
SCHLEGELMILCH, Astronomy, UCLA, Los Angeles, CA, USA; MIWA GOTO, , Max Planck Institute for Extraterrestrial Physics, Munich, Germany; C W WESTRICK, College of Dupage, Glen Ellyn, IL, USA.
Pr
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in
We are nearing completion of a low-resolution 2.0-2.5 µm (4000-5000 cm−1 ) survey of ∼500 very red point-like objects
in the Central Molecular Zone (CMZ) of the Milky Way Galaxy. The goal is to find bright objects with intrinsically featureless
or nearly featureless spectra that are suitable as background light sources for high-resolution infrared absorption spectroscopy
of H+
3 and CO in the Galactic center’s interstellar gas, on sightlines spread across the CMZ. Until recently very few such
objects had been known outside of two clusters of hot and luminous stars close to the very center. We have used Spitzer
Space Telescope 3.6–8.0-µm photometry and 2-Micron All Sky Survey 1.0–2.5-µm photometry to identify candidates with
a significant probability of being stars embedded in circumstellar dust, and over the last several years have been acquiring
low resolution spectra of them to determine their natures. The low resolution spectra, which encompass the wavelengths
of the first overtone band heads of CO, which are prominent in cool stellar photospheres, show that by far the majority of
candidates are very cool and/or highly reddened red giants, which are unsuitable as background sources because of their
complex spectra . However, approximately ten percent of the candidates have featureless or nearly featureless spectra and
are useful for investigations of the interstellar gas. Most of these have continua rising steeply to longer wavelengths and are
luminous, dust embedded stars.
WI08
3:29 – 3:44
CO SPECTRAL LINE ENERGY DISTRIBUTIONS IN ORION SOURCES: TEMPLATES FOR EXTRAGALACTIC OBSERVATIONS
NICK INDRIOLO, EDWIN BERGIN, Department of Astronomy, University of Michigan, Ann Arbor, MI, USA.
The Herschel Space Observatory has enabled the observation of CO emission lines originating in the J = 5 through
J = 48 rotational levels. Surveys of active galaxies (e.g., starbursts, Seyferts, ULIRGs) detect emission from levels as
high as J = 30, but the precise excitation mechanisms responsible for producing the observed CO SLEDs (Spectral Line
Energy Distribution) remain ambiguous. To better constrain the possible excitation mechanisms in extragalactic sources,
we investigate the CO SLEDs arising from sources with known characteristics in the nearby Orion region. Targets include
Orion-KL (high-mass star forming region containing a hot core, embedded protostars, outflows, and shocks), Orion South
(high-mass star forming region containing embedded protostars, outflows, and a photodissociation region), Orion H2 Peak
1 (molecular shock), and the Orion Bar (a photodissociation region). Emission lines from complex sources are decomposed
using velocity information from high spectral resolution observations made with Herschel-HIFI (Heterodyne Instrument for
the Far-Infrared). Each source and/or component is taken as a template for a particular excitation mechanism, and then applied
to interpret excitation in more distant regions within the Galaxy, as well as external galaxies.
Intermission
150
WI09
4:03 – 4:18
+
+
THE DISTRIBUTION, EXCITATION, AND ABUNDANCE OF C , CH , AND CH IN ORION KL
ar
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HARSHAL GUPTA, PATRICK MORRIS, Infrared Processing and Analysis Center, California Institute of Technology, Pasadena, CA, USA; ZSOFIA NAGY, Department of Physics and Astronomy, University of Toledo,
Toledo, OH, USA; JOHN PEARSON, Jet Propulsion Laboratory, California Institute of Technology, Pasadena,
CA, USA; VOLKER OSSENKOPF, I. Physikalisches Institut, Universität zu Köln, Köln, Germany.
in
The CH+ ion was one of the first molecules identified in the interstellar gas over 75 years ago, and is postulated to be a
key species in the initial steps of interstellar carbon chemistry. The high observed abundances of CH+ in the interstellar gas
remain a puzzle, because the main production pathway of CH+ , viz., C+ + H2 → CH+ + H, is so endothermic (4640 K),
that it is unlikely to proceed at the typical temperatures of molecular clouds. One way in which the high endothermicity may
be overcome, is if a significant fraction of the H2 is vibrationally excited, as is the case in molecular gas exposed to intense
far-ultraviolet radiation fields. Elucidating the formation of CH+ in molecular clouds requires characterization of its spatial
distribution, as well as that of the key participants in the chemical pathways yielding CH+ . Here we present high-resolution
spectral maps of the two lowest rotational transitions of CH+ , the fine structure transition of C+ , and the hyperfine-split fine
structure transitions of CH in a ∼ 3′ × 3′ region around the Orion Kleinmann-Low (KL) nebula, obtained with the Herschel
Space Observatory’s Heterodyne Instrument for the Far-Infrared (HIFI).a We compare these maps to those of CH+ and C+
in the Orion Bar photodissociation region (PDR), and discuss the excitation and abundance of CH+ toward Orion KL in the
context of chemical and radiative transfer models, which have recently been successfully applied to the Orion Bar PDR.b
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a
These observations were done as part of the Herschel observations of EXtraordinary sources: the Orion and Sagittarius star-forming regions (HEXOS) Key Programme, led
by E. A. Bergin at the University of Michigan, Ann Arbor, MI.
b
Nagy, Z. et al. 2013, A&A 550, A96
WI10
4:20 – 4:35
+
THE DISTRIBUTION OF SH AROUND ORION KL
HARSHAL GUPTA, Infrared Processing and Analysis Center, California Institute of Technology, Pasadena,
CA, USA; KARL M. MENTEN, Millimeter- und Submillimeter-Astronomie, Max-Planck-Institut für Radioastronomie, Bonn, NRW, Germany; ZSOFIA NAGY, Department of Physics and Astronomy, University of Toledo,
Toledo, OH, USA; PATRICK MORRIS, Infrared Processing and Analysis Center, California Institute of Technology, Pasadena, CA, USA; VOLKER OSSENKOPF, I. Physikalisches Institut, Universität zu Köln, Köln,
Germany; NATHAN CROCKETT, Geological and Planetary Sciences , California Institute of Techonolgy,
Pasadena, CA, USA; JOHN PEARSON, Jet Propulsion Laboratory, California Institute of Technology, Pasadena,
CA, USA.
The SH+ ion is thought to probe energetic processes such as shocks, turbulence, and intense UV fields in interstellar
clouds, because its principal formation route is endothermic by a temperature equivalent of 10117 K—more than twice as
endothermic as that of the well-known ion CH+ . Here we present spectral maps of the lowest fine-structure transitions of
SH+ obtained with the Atacama Pathfinder EXperiment (APEX) telescope over a small (∼ 1′ × 1′ ) region in the vicinity
of the Orion Kleinmann-Low (KL) nebula, the closest chemically rich star-forming region known to contain hot young stars
and shocked gas. Observations of SH+ provide complementary information to those of CH+ (see, e.g., abstract P1303), and
may help assess the role of UV-irradiation vs shocks in the production of SH+ and CH+ , as well as the molecular fraction
and electron density in the regions traced by SH+ and CH+ . We also present chemical and radiative transfer models to help
elucidate the production of SH+ and CH+ , and assess the utility of these ions as probes of processes that regulate the thermal
balance of the interstellar gas and influence star formation in molecular clouds.
151
WI11
CARMA 1 CM LINE SURVEY OF ORION-KL
4:37 – 4:52
ar
y
DOUGLAS FRIEDEL, LESLIE LOONEY, Department of Astronomy, University of Illinois at UrbanaChampaign, Urbana, IL, USA; JOANNA F. CORBY, Department of Astronomy, The University of Virginia, Charlottesville, VA, USA; ANTHONY REMIJAN, ALMA, National Radio Astronomy Observatory, Charlottesville,
VA, USA.
in
We have conducted the first 1 cm (27-35 GHz) line survey of the Orion-KL region by an array. With a primary beam of
∼4.5 arcminutes, the survey looks at a region ∼166,000 AU (0.56 pc) across. The data have a resolution of ∼6 arcseconds
on the sky and 97.6 kHz(1.07-0.84 km/s) in frequency. This region of frequency space is much less crowded than at 3mm
or 1mm frequencies and contains the fundamental transitions of several complex molecular species, allowing us to probe the
largest extent of the molecular emission. We present the initial results, and comparison to 3mm results, from several species
including, dimethyl ether [(CH3 )2 O], ethyl cyanide [C2 H5 CN], acetone [(CH3 )2 CO], SO, and SO2 .
WI12
CHEMICAL COMPLEXITY IN THE SHOCKED OUTFLOW L1157-B REVEALED BY CARMA
4:54 – 5:09
Pr
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NIKLAUS M DOLLHOPF, Department of Astronomy, The University of Virginia, Charlottesville, VA, USA;
BRETT A. McGUIRE, NAASC, National Radio Astronomy Observatory, Charlottesville, VA, USA; BRANDON
CARROLL, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA,
USA; ANTHONY REMIJAN, ALMA, National Radio Astronomy Observatory, Charlottesville, VA, USA.
We present results from a targeted chemical search toward the prototypical shocked outflow L1157. L1157-B0, -B1, and
-B2 are shocked regions within the outflow from the Class 0 low-mass protostar L1157-mm. We have mapped a variety of
molecular tracers in the region with typical spatial resolutions of ∼ 3′′ using CARMA, and find differences in the chemical
makeups between shocked regions within the same precursor outflow material. We present observations of CH3 OH, HCO+ ,
HCN, and the first maps of HNCO in the source. We will examine the utility of HNCO as a sensitive tracer of the shocks in
this source, and finally, we will discuss what insights we can gain into the chemical evolution, and evolutionary time scales,
that have given rise to the differentiation we see between the shocks.
WI13
5:11 – 5:26
THE CURIOUS CASE OF NH2 OH: HUNTING A DIRECT AMINO ACID PRECURSOR SPECIES IN THE INTERSTELLAR MEDIUM
BRETT A. McGUIRE, NAASC, National Radio Astronomy Observatory, Charlottesville, VA, USA; BRANDON
CARROLL, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena,
CA, USA; NIKLAUS M DOLLHOPF, Department of Astronomy, The University of Virginia, Charlottesville, VA,
USA; NATHAN CROCKETT, Geological and Planetary Sciences , California Institute of Techonolgy, Pasadena,
CA, USA; GEOFFREY BLAKE, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA; ANTHONY REMIJAN, ALMA, National Radio Astronomy Observatory, Charlottesville, VA, USA.
Despite the detection of amino acids, the building blocks of the proteins that support life, in cometary and meteoritic
samples, we do not yet understand the conditions under which these life-essential species have formed. Hydroxylamine
(NH2 OH) is potentially a direct precursor to the formation of the amino acids glycine and alanine in the ISM, through
reaction with acetic and propionic acids. Recent laboratory and modeling work has shown that there are a variety of pathways
to the formation of NH2 OH in interstellar ices both efficiently and in high abundance. Here, we present the result of a deep,
multi-telescope search for NH2 OH in the shocked, complex molecular source L1157. We find no evidence suggesting the
presence of this important precursor, and discuss the implications of this non-detection on the reactivity of NH2 OH both
within the ices, and in the gas-phase ISM. We will also discuss how these observations should inform the direction of future
studies, both in the laboratory and with state-of-the-art telescopes such as ALMA.
152
WI14
NEW RESULTS FROM THE CARMA LARGE-AREA STAR FORMATION SURVEY (CLASSY)
5:28 – 5:43
ar
y
ROBERT J HARRIS, LESLIE LOONEY, DOMINIQUE M. SEGURA-COX, Department of Astronomy, University of Illinois at Urbana-Champaign, Urbana, IL, USA; MANUEL FERNANDEZ-LOPEZ, Instituto Argentino de Radioastronomı́a, Centro Cientı́fico Tecnológico La Plata, Villa Elisa, Argentina; LEE MUNDY,
SHAYE STORM, MAXIME RIZZO, Department of Astronomy, University of Maryland, College Park, MD,
USA; KATHERINE LEE, Radio and Geoastronomy Division, Harvard-Smithsonian Center for Astrophysics,
Cambridge, MA, USA; HÉCTOR ARCE, Astronomy Department, Yale University, New Haven, CT, USA.
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Interferometric imaging spectroscopy of molecular clouds permits the physical and thermodynamic structure, kinematics,
and chemistry of molecular clouds to be probed over a wide range of spatial scales, from entire clouds to the individual cores
where stars are born. As such, it allows the study of what fundamental physical processes are at play in star formation. The
CARMA Large Area Star-formation Survey (CLASSy) Key Project surveyed dense gas tracers (the HCN, HCO+, and N2 H+
J=1-0 emission) and dust continuum emission over 700 square arc-minutes from 3 fields in Perseus (NGC 1333, Barnard 1,
and L1451) and 2 fields in Serpens (Serpens Main and Serpens South), with sensitivity to structures on spatial scales ranging
from 1000 AU to several parsecs. We have used these data to characterize the importance of turbulence and magnetic fields
in star formation on physical scales ranging from the largest clouds to the immediate environment of individual young stellar
objects. We present results from both CLASSy and a significant extension of this project, CLASSy Prime, to more deeply
survey these regions in both the same and different tracers, including several organic molecules. In particular, we focus on
discrepancies between the structure of filaments seen in line emission – particularly N2 H+ – and the same filaments seen
in dust emission, and we suggest that these might be due to excitation conditions and/or chemical effects. We also discuss
how emission from the different molecules that have been observed with CLASSy Prime highlight kinematics of different
substructures within these regions.
WI15
ADMIT: ALMA DATA MINING TOOLKIT
5:45 – 6:00
DOUGLAS FRIEDEL, LESLIE LOONEY, Department of Astronomy, University of Illinois at UrbanaChampaign, Urbana, IL, USA; LISA XU, NCSA, University of Illinois at Urbana-Champaign, Urbana, IL,
USA; MARC W. POUND, PETER J. TEUBEN, KEVIN P. RAUCH, LEE MUNDY, Department of Astronomy,
University of Maryland, College Park, MD, USA; JEFFREY S. KERN, NRAO, NRAO, Socorro, NM, USA.
ADMIT (ALMA Data Mining Toolkit) is a toolkit for the creation and analysis of new science products from ALMA
data. ADMIT is an ALMA Development Project written purely in Python. While specifically targeted for ALMA science
and production use after the ALMA pipeline, it is designed to be generally applicable to radio-astronomical data. ADMIT
quickly provides users with a detailed overview of their science products: line identifications, line ’cutout’ cubes, moment
maps, emission type analysis (e.g., feature detection), etc. Users can download the small ADMIT pipeline product (<20MB),
analyze the results, then fine-tune and re-run the ADMIT pipeline (or any part thereof) on their own machines and interactively
inspect the results. ADMIT will have both a GUI and command line interface available for this purpose. By analyzing multiple
data cubes simultaneously, data mining between many astronomical sources and line transitions will be possible. Users will
also be able to enhance the capabilities of ADMIT by creating customized ADMIT tasks satisfying any special processing
needs. Future implementations of ADMIT may include EVLA and other instruments.
153
WJ. Non-covalent interactions
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Chair: Wolfgang Jäger, University of Alberta, Edmonton, AB, Canada
in
WJ01
1:30 – 1:45
FORMATION OF COMPLEXES c-C3 H6 ···MCl (M = Ag or Cu) AND THEIR CHARACTERIZATION BY BROADBAND
ROTATIONAL SPECTROSCOPY
DANIEL P. ZALESKI, JOHN CONNOR MULLANEY, NICK WALKER, School of Chemistry, Newcastle University, Newcastle-upon-Tyne, United Kingdom; ANTHONY LEGON, School of Chemistry, University of Bristol, Bristol, United Kingdom.
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New molecules formed by the non-covalent interaction of cyclopropane (c-C3 H6 ) with MCl, where M is either Ag or
Cu, have been detected and characterized by means of broadband rotational spectroscopy. They were synthesized by laser
ablation of a silver or copper rod in the presence of a gaseous sample containing 1% each of c-C3 H6 and CCl4 , with the
remainder argon. Spectra of several isotopologues of each complex have been analysed. The title molecules are found to have
C2v symmetry, and the geometry can be described by the MCl subspecies coordinating “edge on” to the cyclopropane ring.
Experimental structures will be compared with those from ab initio calculations and those of related species.
WJ02
1:47 – 2:02
ROTATIONAL SPECTROSCOPY OF MONOFLUOROETHANOL AGGREGATES WITH ITSELF AND WITH WATER
JAVIX THOMAS, WENYUAN HUANG, XUNCHEN LIUa , WOLFGANG JÄGER, YUNJIE XU, Department
of Chemistry, University of Alberta, Edmonton, AB, Canada.
Fluoroalcohols are used as common cosolvents for studies of the secondary and tertiary substructures of polypeptides and
proteins in aqueous solution. It has been proposed that small fluoroalcohol aggregates are crucial for the protein structural
altering process.[1] A rotational spectroscopic study of the monofluoroethanol (MFE) dimer was reported by our group
before.[2] In this presentation, we report our recent results on the MFE trimer and MFE-water clusters. We analyze the
competitive formation of intra- and intermolecular hydrogen bonds, processes that may be crucial for the changes in protein
structure that occur in fluoroalcohol-water solution. We show that the MFE trimer takes on a much different binding topology
from the recently reported phenol trimer.[3] The results will also be compared to the closely related 2,2,2-trifluoroethanol
systems.
[1] H. Reiersen, A. R. Rees, Protein Eng. 2000, 13, 739 – 743. [2] X. Liu, N. Borho, Y. Xu, Chem. Eur. J. 2009, 15, 270
– 277. [3] a) N. A. Seifert, A. L. Steber, J. L. Neill, C. Pérez, D. P. Zaleski, B. H. Pate, A. Lesarri, Phys. Chem. Chem. Phys.,
2013, 15, 11468; b) T. Ebata, T. Watanabe, N. Mikami, J. Phys. Chem., 1995, 99, 5761.
a
Permanent address: Mechanical Department, Shanghai Jiao Tong University, Shanghai, P. R. China.
154
WJ03
2:04 – 2:19
O-TOLUIC ACID MONOMER AND MONOHYDRATE: ROTATIONAL SPECTRA, STRUCTURES, AND ATMOSPHERIC IMPLICATIONS
ar
y
ELIJAH G SCHNITZLER, BRANDI L M ZENCHYZEN, WOLFGANG JÄGER, Department of Chemistry,
University of Alberta, Edmonton, AB, Canada.
a
b
c
in
Clusters of carboxylic acids with water, sulfuric acid, and other atmospheric species potentially increase the rate of new
particle formation in the troposphere.a,b Here, we present high-resolution pure rotational spectra of o-toluic acid and its
complex with water in the range of 5-14 GHz, measured with a cavity-based molecular beam Fourier-transform microwave
spectrometer. In both the monomer and the complex, the carboxylic acid functional group adopts a syn- conformation, with
the acidic proton oriented away from the aromatic ring. In the complex, water participates in two hydrogen bonds, forming
a six-membered intermolecular ring. Despite its large calculated c-dipole moment, no c-type transitions were observed
for the complex, because of a large amplitude “wagging” motion of the unbound hydrogen of water, similar to the case
of the benzoic acid-water complex.c No methyl internal rotation splittings were observed, consistent with a high barrier
(7 kJ mol−1 ) calculated for the monomer at the B3LYP/6-311++G(d,p) level of theory. Using statistical thermodynamics,
experimental rotational constants were combined with a theoretical frequency analysis and binding energy to give an estimate
of the percentage of hydrated acid in the atmosphere under various conditions.
F. Riccobono, et al., Science, 344, 717 (2014).
R. Zhang, et al., Science, 304, 1487 (2004).
E. G. Schnitzler and W. Jäger, Phys. Chem. Chem. Phys., 16, 2305 (2014).
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WJ04
2:21 – 2:36
A ROVIBRATIONAL ANALYSIS OF THE WATER BENDING VIBRATION IN OC-H2 O AND A MORPHED POTENTIAL OF THE COMPLEX
LUIS A. RIVERA-RIVERA, SEAN D. SPRINGER, BLAKE A. McELMURRY, Department of Chemistry,
Texas A & M University, College Station, TX, USA; IGOR I LEONOV, Microwave Spectroscopy, Institute of
Applied Physics, Nizhny Novgorod, Russia; ROBERT R. LUCCHESE, JOHN W. BEVAN, Department of Chemistry, Texas A & M University, College Station, TX, USA; L. H. COUDERT, LISA, CNRS, Universités Paris Est
Créteil et Paris Diderot, Créteil, France.
Rovibrational transitions associated with tunneling states in the water bending vibration in OC-H2 O complex have been
recorded using a supersonic jet quantum cascade laser spectrometer at 6.2 µm. Analysis of the resulting spectra is facilitated
by incorporating fits of previously recorded microwave and submillimeter data accounting for Coriolis coupling to obtain
the levels of the ground vibrational state. The results were then used to confirm assignment of the vibration and explore the
nature of tunneling dynamics in associated vibrationally excited states of the complex. A seven-dimension ab initio interaction
potential is constructed for the complex. The available spectroscopic data is used to generated a morphed potential. Previous
prediction of the D0 of the complex will be incorporated in the analysis.
WJ05
2:38 – 2:53
THE MICROWAVE SPECTRUM AND UNEXPECTED STRUCTURE OF THE BIMOLECULAR COMPLEX FORMED
BETWEEN ACETYLENE AND (Z)-1-CHLORO-2-FLUOROETHYLENE
NAZIR D. KHAN, HELEN O. LEUNG, MARK D. MARSHALL, Chemistry Department, Amherst College,
Amherst, MA, USA.
In all previously studied complexes between protic acids and chlorofluoroethylenes in our laboratory, the acidic hydrogen
atom forms the primary intermolecular interaction with a fluorine atom on the ethylene subunit. This has been rationalized by
the greater electronegativity of the fluorine atom leading to a stronger, hydrogen-bond like interaction, than would be formed
with the chlorine atom. With (Z)-1-chloro-2-fluoroethylene, however, ab initio calculations for its complex with acetylene
indicate that participation of the chlorine atom in the intermolecular interaction leads to lower energy configurations. This
is confirmed by observation of the rotational spectrum of the complex by chirped-pulse and Balle-Flygare Fourier transform
microwave spectroscopy. The complex is determined to be planar with one interaction between an acetylenic hydrogen and
the chlorine atom and a second between the triple bond and the hydrogen atom geminal to chlorine.
155
WJ06
2:55 – 3:10
CHLORINE NUCLEAR QUADRUPOLE HYPERFINE STRUCTURE IN THE VINYL CHLORIDE–HYDROGEN CHLORIDE COMPLEX
ar
y
HELEN O. LEUNG, MARK D. MARSHALL, JOSEPH P. MESSINGER, Chemistry Department, Amherst College, Amherst, MA, USA.
Pr
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The microwave spectrum of the vinyl chloride–hydrogen chloride complex, presented at last year’s symposium, is greatly
complicated by the presence of two chlorine nuclei as well as an observed, but not fully explained tunneling motion. Indeed, although it was possible at that time to demonstrate conclusively that the complex is nonplanar, the chlorine nuclear
quadrupole hyperfine splitting in the rotational spectrum resisted analysis. With higher resolution, Balle-Flygare Fourier
transform microwave spectra, the hyperfine structure has been more fully resolved, but appears to be perturbed for some rotational transitions. It appears that knowledge of the quadrupole coupling constants will provide essential information regarding
the structure of the complex, specifically the location of the hydrogen atom in HCl. Our progress towards obtaining values
for these constants will be presented.
WJ07
3:12 – 3:27
ELECTRONIC COMMUNICATION IN COVALENTLY vs. NON-COVALENTLY BONDED POLYFLUORENE SYSTEMS: THE ROLE OF THE COVALENT LINKER.
BRANDON UHLER, NEIL J REILLY, MARAT R TALIPOV, MAXIM IVANOV, QADIR TIMERGHAZIN,
RAJENDRA RATHORE, SCOTT REID, Department of Chemistry, Marquette University, Milwaukee, WI, USA.
H
C
HC
C
HC
H
C
CH2•
CH
C
H
benzyl radical
~
X 2B1
HC
•
HC
C
H
H
C•
CH
CH
CH
tropyl radical
~
X 2E2"
HC
C
HC
H
H
C
CH
C
H
norboradienyl radical
~
X 2B1
The covalently linked polyfluorene molecules F1-F6 (see left) are prototypical molecular wires by
virtue of their favorable electron/hole transport properties brought about by π-stacking. To understand
the role of the covalent linker in facilitating electron transport in these systems, we have investigated
several van der Waals (vdW) analogues by resonant mass spectroscopy. Electronic spectra and ion
yield curves are reported for jet-cooled vdW clusters containing up to six fluorene units. The nearcoincidence of the electronic band origins for the dimer and larger clusters suggests that a structure
containing a central dimer chromophore is the predominant conformational motif. As for F1-F6,
the threshold ionization potentials extracted from the ion yield measurements decrease linearly with
inverse cluster size. Importantly, however, the rate of decrease is significantly smaller in the vdW
clusters, indicating more efficient hole stabilization in the covalently bound systems. Results for
similar vdW clusters that are locked into specific conformations by steric effects will also be reported.
Intermission
156
WJ08
3:46 – 4:01
A GENERAL TRANSFORMATION TO CANONICAL FORM FOR POTENTIALS IN PAIRWISE INTERMOLECULAR
INTERACTIONS
ar
y
JAY R. WALTON, Department of Mathematics, Texas A & M University, College Station, TX, USA; LUIS A.
RIVERA-RIVERA, ROBERT R. LUCCHESE, JOHN W. BEVAN, Department of Chemistry, Texas A & M University, College Station, TX, USA.
Pr
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A generalized formulation of explicit transformations is introduced to investigate the concept of a canonical potential in
both fundamental chemical and intermolecular bonding. Different classes of representative ground electronic state pairwise
interatomic interactions are referenced to a single canonical potential illustrating application of explicit transformations.
Specifically, accurately determined potentials of the diatomic molecules H2 , H+2 , HF, LiH, argon dimer, and one-dimensional
dissociative coordinates in Ar-HBr, OC-HF, and OC-Cl2 are investigated throughout their bound potentials. The advantages
of the current formulation for accurately evaluating equilibrium dissociation energies and a fundamentally different unified
perspective on nature of intermolecular interactions will be emphasized. In particular, this canonical approach has relevance
to previous assertions that there is no very fundamental distinction between van der Waals bonding and covalent bonding or
for that matter hydrogen and halogen bonds.
WJ09
4:03 – 4:18
THREE-DIMENSIONAL WATER NETWORKS SOLVATING AN EXCESS POSITIVE CHARGE: NEW INSIGHTS INTO
THE MOLECULAR PHYSICS OF ION HYDRATION
CONRAD T. WOLKE, JOSEPH FOURNIER, Department of Chemistry, Yale University, New Haven, CT, USA;
GARY H WEDDLE, Department of Chemistry and Biochemistry, Fairfield University, Fairfield, CT, USA;
EVANGELOS MILIORDOS, SOTIRIS XANTHEAS, Physical Sciences Division, Pacific Northwest National
Laboratory, Richland, WA, USA; MARK JOHNSON, Department of Chemistry, Yale University, New Haven,
CT, USA.
In a recent effort our group investigated the vibrational mechanics of water using the cage of 20 water molecules surrounding an alkali ion as a paradigm system. The M+ (H2 O)20 clusters are well known “magic number” species (for the larger
alkali metals) and are thought to form a pentagonal dodecahedral web encapsulating the ion. We are attracted to these systems
because they are sufficiently large to display broad OH fundamental envelopes in a manner similar to that found in bulk water,
but do so with a relatively small number of structurally distinct, three coordinated sites in a finite assembly that, although
challenging, can be analyzed with electronic structure calculations in the context of a “supermolecule”. We show how this
arrangement can provide an ideal platform on which to unambiguously identify the spectral signatures of particular binding
sites, information that is invoked to explain the bulk (and interface) spectrum of water but cannot be directly measured in bulk
water.
Although this behavior is most relevant to simulations of interfacial water, a future direction of this study will be gaining
site-specific information for water in an extended two dimensional structure, and the elucidation of the paths of spectral
diffusion associated with this arrangement. This unprecedented work will clarify a number of open questions regarding the
site-specificity of ground and vibrationally excited state dynamics.
157
WJ10
4:20 – 4:35
MATRIX ISOLATION INFRARED SPECTROSCOPY OF A SERIES OF 1:1 PHENOL-WATER COMPLEXES
PUJARINI BANERJEE, TAPAS CHAKRABORTY, Physical Chemistry, Indian Association for the Cultivation
of Science, Kolkata, India.
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We report here the FTIR spectra of 1:1 complexes of eight fluorophenol derivatives with water measured under matrix
isolation condition. In all the complexes, oxygen of water is the hydrogen bond acceptor and phenolic O-H the hydrogen
bond donor. The attributes of the O-H...O linkage in the complexes are tuned remotely by fluorine substitutions at different
aromatic sites of phenol. The goal of the study is to find the intermolecular interactions that correlate best with the sequence
of spectral shifts of the donor O-H stretching (νOH ) frequencies. Measurements reveal that the probe phenolic νOH shifts
vary by nearly 90% from unsubstituted phenol to pentafluorophenol. Interestingly, this large variation correlates poorly with
the predicted binding energies of the complexes. Secondly, although electrostatic interaction is considered to dominate the
overall stabilization of such classical hydrogen bonds, we see that the shifts do not display any correlation with this interaction
at the hydrogen bonding sites. On the other hand, the purely quantum mechanical charge-transfer interaction energies, as
obtained from Natural Bond Orbital analysis,are found to display very good correspondence with the spectral shifts. Thus,
we propose that such local charge-transfer type interactions are better descriptors of weakening of the hydrogen bond donor
than electrostatic energy parameters.
WJ11
4:37 – 4:52
MATRIX ISOLATION IR SPECTROSCOPY AND QUANTUM CHEMISTRY STUDY OF 1:1 Π-HYDROGEN BONDED
COMPLEXES OF BENZENE WITH A SERIES OF FLUOROPHENOLS
O-H stretching infrared fundamentals (νOH ) of phenol and a series of fluorophenol monomers and their 1:1 complexes
with benzene have been measured under a matrix isolation condition (8K). For the phenol-benzene complex the measured
shift of νOH is 78 cm−1 and for 3, 4, 5-trifluorophenol it is 98 cm−1 . Although the cold matrix isolation environment is very
different from an aqueous medium, the measured spectral shifts display an interesting linear correlation with the aqueous
phase acid dissociation constants (pKa ) of the phenols. The spectral shifts predicted by quantum chemistry calculations
at several levels of theory are consistent with the observed values. Correlations of the shifts are also found with respect to
energetic, geometric and several other electronic structure parameters of the complexes. Partitioning of binding energies of the
complexes into components following the Morokuma-Kitaura scheme shows that dispersion is the predominant component
of attractive interaction, and electrostatics, polarization and charge-transfer terms also have contributions to overall binding
stability. NBO analysis reveals that hyperconjugative charge-transfers from the filled π-orbitals of the hydrogen bond acceptor
(benzene) to the anti-bonding σ*(O–H) orbital of the donors (phenols) display correlations which are fully consistent with the
observed variations of spectral shifts. The analysis also shows that the O-H bond dipole moments of all the phenolic species
are nearly the same, implying that local electrostatics has only a little effect at the site of hydrogen bonding.
158
WJ12
4:54 – 5:09
MATRIX ISOLATION IR SPECTROSCOPY OF 1:1 COMPLEXES OF ACETIC ACID AND TRIHALOACETIC ACIDS
WITH WATER AND BENZENE
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A comparative study of infrared spectral effects for 1:1 complex formation of acetic acid (AA), trifluoroacetic acid
(TFAA) and trichloroacetic acid (TFAA) with water and benzene has been carried out under a matrix isolation environment.
Despite the large difference in aqueous phase acidities of the three acids, the measured νOH stretching frequencies of the
monomers of the three molecules are found to be almost same, and in agreement with gas phase electronic structure calculations. Intrinsic acidities are expressed only in the presence of the proton acceptors, water or benzene. Although electronic
structure calculations predict distinct νOH red-shifts for all three acids, the measured spectral features for TCAA and TFAA
in this range do not allow unambiguous assignments for the 1:1 complex. On the other hand, the spectral changes in the
νC=O region are more systematic, and the observed changes are consistent with predictions of theory. Components of overall
binding energy of each complex have been obtained from energy decomposition analysis, which allows determination of the
relative contributions of various physical forces towards overall stability of the complexes, and the details will be discussed
in the talk.
WJ13
5:11 – 5:21
SPECTROSCOPIC INVESTIGATION OF THE EFFECTS OF ENVIRONMENT ON NEWLY-DEVELOPED NEAR INFRARED EMITTING DYES
LOUIS E. McNAMARA, NALAKA LIYANAGE, Chemistry and Biochemistry, University of Mississippi, Oxford, MS, USA; JARED DELCAMP, Chemistry, University of Mississippi, Oxford, MS, USA; NATHAN I HAMMER, Chemistry and Biochemistry, University of Mississippi, Oxford, MS, USA.
The effects of environment on the photophysical properties of a series of newly-developed near infrared emitting dyes
was studied spectroscopically. Properties of interest include fluorescence emission, fluorescence lifetime, and quantum yield.
Tracking how the photophysics of these compounds are affected in the solid phase, in thin films, in solution, and at the single
molecule level with changing environment will provide a deeper insight into how dye structure affects their function.
159
WJ14
5:23 – 5:38
SPECTROSCOPIC SIGNATURES AND STRUCTURAL MOTIFS IN ISOLATED AND HYDRATED XANTHINE AND
ITS METHYLATED DERIVATIVES
VIPIN BAHADUR SINGH, Department of Physics, Udai Pratap Autonomous College, Varanasi, India.
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The conformational landscapes of neutral xanthine and its methylated derivatives and their hydrated complexes have
been investigated by MP2 and DFT methods. We investigated the low-lying excited states of bare xanthine , theophylline,
theobromine and caffeine by means of coupled cluster singles and approximate doubles (CC2) and TDDFT methods and a
satisfactory interpretation of the electronic absorption spectra1 is obtained. One striking feature is the coexistence of the blue
and red shift of the vertical excitation energy of the optically bright state S1 (1pipi* ) of xanthine, caffeine2 and theophylline3
upon forming complex with a water at C2=O and C6=O carbonyl sites, respectively. The lowest singlet pipi* excited-state of
the caff1-(H2O)1 complex involving isolated carbonyl are strongly blue shifted which is in agreement with the result of R2PI
spectra of singly hydrated caffeine.4 While for the most stable and the second most stable caff1-(H2O)1 complexes involving
conjugated carbonyl, the lowest singlet pipi* excited-state is red shifted. The effect of hydration on S1 ( 1pipi* ) excited state
due to bulk water environment was mimicked by a combination of PCM and COSMO models, which also shows a blue shift
in accordance with the result of electronic absorption spectra in aqueous solution.1 This hypsochromic shift, is expected to be
the result of the changes in the pi-electron delocalization extent of molecule because of hydrogen bond formation. We have
also clarified that the intermolecular hydrogen-bond strengthening and weakening correspond to red shifts and blue shifts,
respectively, in the electronic spectra. It is expected that the radiation less deactivation is dramatically influenced through
the regulation of electronic states by strong hydrogen bonding interaction. The optimized structure of newly characterized
theophylline dimer Form IV,computed the first time by MP2 and DFT methods. The binding energy of this dimer linked by
double N-H. . . O=C hydrogen bonds was found to be 88 kj/mole at the MP2/6-311++G(d,p) level of theory.3 Computed IR
spectra is found in remarkable agreement with the experiment and the out of phase (C=O)2 stretching mode shows tripling of
intensity upon dimerisation. 1. J. Chen and B.Kohler, Phys. Chem. Chem. Phys., 2012, 14, 10677-10682 2. Vipin Bahadur
Singh, RSC.Adv.,2014,4,58116-58126 3. Vipin Bahadur Singh, RSC.Adv.,2015,5,11433-11444 4. D. Kim, H. M. Kim, K.
Y.Yang, S. K. Kim and N. J. Kim, J.Chem.Phys. 2008, 128, 134310-134316
160
RA. Metal containing
Chair: Damian L Kokkin, Arizona State University, Tempe, Arizona, USA
8:30 – 8:45
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RA01
1
+
HYPERFINE RESOLVED PURE ROTATIONAL SPECTROSCOPY OF ScN, YN, AND BaNH (X Σ ): INSIGHT INTO
METAL-NITROGEN BONDING
LINDSAY N. ZACK, Department of Chemistry, Wayne State University, Detroit, MI, USA; MATTHEW
BUCCHINO, Department of Chemistry and Astronomy, University of Arizona, Tucson, AZ, USA; JUSTIN
YOUNG, MARSHALL BINNS, PHILLIP M. SHERIDAN, Department of Chemistry and Biochemistry, Canisius College, Buffalo, NY, USA; LUCY ZIURYS, Department of Chemistry and Biochemistry, University of
Arizona, Tucson, AZ, USA.
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Fourier transform microwave spectroscopy coupled with a discharge-assisted laser ablation source (DALAS) has been
used to record the J = 1 → 0 pure rotational transitions of Sc14 N, Sc15 N, Y14 N, Y15 N, and Ba14 NH (X1 Σ+ ). Each species
was synthesized by the reaction of the ablated metal with either NH3 or 15 NH3 in the presence of a DC discharge. For each
species hyperfine structure was resolved. In the case of ScN and YN hyperfine parameters (quadrupole and nuclear spinrotation) for the metal and nitrogen were determined and for BaNH the nitrogen quadrupole coupling constant was measured.
These hyperfine constants are interpreted to gain insight into the metal-nitrogen bonding in each species. In addition, DFT
calculations were performed to assist with the assignment of each spectrum and the characterization of the metal-nitrogen
bond.
RA02
1
+
8:47 – 9:02
6
+
+
3
−
THE SUBMILLIMETER/THz SPECTRUM OF AlH (X Σ ), CrH (X Σ ), and SH (X Σ )
DeWAYNE T HALFEN, Department of Chemistry and Astronomy, University of Arizona, Tucson, AZ, USA;
LUCY ZIURYS, Department of Chemistry and Biochemistry, University of Arizona, Tucson, AZ, USA.
The N = 2 ← 1 transition of the CrH (X6 Σ+ ) radical near 730-734 GHz and the J = 2 ← 1 line of AlH (X1 Σ+ ) near 755
GHz have been measured using submillimeter/Terahertz direct absorption spectroscopy. CrH was created in an AC discharge
of Cr(CO)6 vapor and H2 in the presence of argon. AlH was produced from Al(CH3 )3 vapor and H2 in argon with an AC
discharge. In addition, three fine structure components of the N = 1 ← 0 transition of the SH+ (X3 Σ− ) cation from 345683 GHz were recorded. SH+ was generated from H2 S and argon in an AC discharge. The data have been analyzed, and
spectroscopic constants for these species have been refined. These parameters are in excellent agreement with past millimeter,
infrared, and optical data. SH+ is a known interstellar molecule, and these measurements confirm recent observations of this
species. The new data for CrH and AlH could facilitate the detection of these species in interstellar/circumstellar gas.
RA03
9:04 – 9:19
FORMATION OF M-C≡C-Cl (M = Ag or Cu) AND CHARACTERIZATION BY ROTATIONAL SPECTROSCOPY
DANIEL P. ZALESKI, School of Chemistry, Newcastle University, Newcastle-upon-Tyne, United Kingdom;
DAVID PETER TEW, School of Chemistry, University of Bristol, Bristol, United Kingdom; NICK WALKER,
School of Chemistry, Newcastle University, Newcastle-upon-Tyne, United Kingdom; ANTHONY LEGON,
School of Chemistry, University of Bristol, Bristol, United Kingdom.
The new linear molecule Ag-C≡C-Cl has been detected and characterized by means of rotational spectroscopy. It was
synthesized by laser ablation of a silver rod in the presence of a gaseous sample containing a low concentration of CCl4
in argon, cooled to a rotational temperature approaching 2 K through supersonic expansion and analyzed by chirped pulse
Fourier transform microwave spectroscopy. Substitution coordinates are available for the silver and chlorine positions and
will be compared to ab initio calculations at the CCSD(T)/aug-cc-pV5Z level of theory. The Ag-13 C≡13 C-Cl isotopologue
was also observed using a similar gas mixture containing 13 CCl4 . The Cu analogue Cu-C≡C-Cl was similarly identified and
characterized.
161
RA04
9:21 – 9:36
(CH3 )3 N···AgI AND H3 N···AgI STUDIED BY BROADBAND ROTATIONAL SPECTROSCOPY AND AB INITIO CALCULATIONS
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DROR M. BITTNER, DANIEL P. ZALESKI, SUSANNA L. STEPHENS, NICK WALKER, School of Chemistry, Newcastle University, Newcastle-upon-Tyne, United Kingdom; ANTHONY LEGON, School of Chemistry,
University of Bristol, Bristol, United Kingdom.
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The pure rotational spectra of 8 isotopologues of H3 N···AgI and 6 isotopologues of (CH3 )3 N···AgI were measured in a
chirped pulse Fourier-transform microwave spectrometer. The complexes were synthesized in a molecular beam from a gas
sample containing H3 N or (CH3 )3 N and CF3 I precursors diluted in argon. Laser ablation was used to introduce silver atoms to
the gas phase. The rotational constant B0 , centrifugal distortion constants DJ and DJK , and the nuclear quadrupole coupling
constant χaa (I) have been determined for (CH3 )3 14/15 N···107/109 AgI, (CD3 )3 N···107/109 AgI, H3 14/15 N···107/109 AgI and
D3 N···107/109 AgI by fitting the measured transitions to a symmetric top Hamiltonian. The spectroscopic constants (B0 + C0 ),
∆J and χaa (I) have been determined for D2 HN···107/109 AgI through fits that employed a Hamiltonian appropriate for a very
near prolate asymmetric rotor. Partial effective (r0 ) and substitution (rs ) structures have been determined.
RA05
MICROWAVE SPECTRA AND GEOMETRIES OF C2 H2 · · · AgI and C2 H4 · · · AgI
9:38 – 9:53
SUSANNA L. STEPHENS, Department of Chemistry, University of Manitoba, Winnipeg, MB, Canada; DAVID
PETER TEW, School of Chemistry, University of Bristol, Bristol, United Kingdom; NICK WALKER, School
of Chemistry, Newcastle University, Newcastle-upon-Tyne, United Kingdom; ANTHONY LEGON, School of
Chemistry, University of Bristol, Bristol, United Kingdom.
A chirped-pulse Fourier transform microwave spectrometer has been used to measure the microwave spectra of both
C2 H2 · · · AgI and C2 H4 · · · AgI. These complexes are generated via laser ablation at 532 nm of a silver surface in the
presence of CF3 I and either C2 H2 or C2 H4 and argon and are stabilized by a supersonic expansion. Rotational (A0 , B0 ,
C0 ) and centrifugal distortion constants (∆J and ∆JK ) of each molecule have been determined as well the nuclear electric
quadrupole coupling constants the iodine atom (χaa (I) and χbb − χcc (I)). The spectrum of each molecule is consistent with
a C2v structure in which the metal atom interacts with the π-orbital of the ethene or ethyne molecule. Isotopic substitutions
of atoms within the C2 H2 or C2 H4 subunits are in progress and in conjunction with high level ab initio calculations will
allow for accurate determination of the geometry of each molecule. These to complexes are put in the context of the recently
studied H2 S · · · AgI,a OC· · · AgI,b , H3 N · · · AgI and (CH3 )3 N · · · AgI.c
a
b
c
S.Z. Riaz, S.L. Stephens, W. Mizukami, D.P. Tew, N.R. Walker, A.C. Legon, Chem. Phys. Let., 531, 1-12 (2012)
S.L. Stephens, W. Mizukami, D.P. Tew, N.R. Walker, A.C. Legon, J. Chem. Phys., 136(6), 064306 (2012)
D.M. Bittner, D.P. Zaleski, S.L. Stephens, N.R. Walker, A.C. Legon, Study in progress.
Intermission
162
RA06
10:12 – 10:27
+
EVALUATION OF THE EXOTHERMICITY OF THE CHEMI-IONIZATION REACTION Sm + O → SmO + e−
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RICHARD M COX, JUNGSOO KIM, PETER ARMENTROUT, Department of Chemistry, University of Utah,
Salt Lake City, UT, USA; JOSHUA BARTLETT, ROBERT A. VANGUNDY, MICHAEL HEAVEN, Department
of Chemistry, Emory University, Atlanta, GA, USA; JOSHUA J. MELKO, Department of Chemistry, University of
North Florida, Jacksonville, FL, USA; SHAUN ARD, NICHOLAS S. SHUMAN, ALBERT VIGGIANO, Space
Vehicles Directorate, Air Force Research Lab, Kirtland AFB, NM, USA.
in
The chemi-ionization reaction Sm + O → SmO+ + e− has been used for chemical release experiments in the thermosphere. This reaction was chosen, in part, because the best available data indicated that it is exothermic by 0.35 ± 0.12
eV. Low ion yields in the initial atmospheric release experiments raised questions concerning the accuracy of the ionization
energy (IE) for SmO and the bond dissociation energy (BDE) of SmO+ . New measurements of the BDE, obtained using a
selected ion flow tube and guided ion beam techniques, yielded a more precise value of 5.73 ± 0.07 eV. The ionization energy
of SmO was reexamined using pulsed-field ionization zero kinetic energy (ZEKE) photoelectron spectroscopy. The value
obtained, 5.7427 ± 0.0006 eV, was significantly higher than the literature value. Combined with literature bond energies
of SmO, this IE indicates an exothermicity for Sm + O → SmO+ + e− of 0.14 ± 0.17 eV, independent from and in agreement with the value deduced from the guided ion beam measurements. The implications of these results for interpretation of
chemical release experiments are considered.
RA07
10:29 – 10:44
The PERMANENT ELECTRIC DIPOLE MOMENT AND HYPERFINE INTERACTION IN GOLD SULFIDE, AuS
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RUOHAN ZHANG, DAMIAN L KOKKIN, Department of Chemistry and Biochemistry, Arizona State University, Tempe, AZ, USA; THOMAS D. VARBERG, Chemistry Department , Macalester College, Saint Paul,
Minnesota, USA; TIMOTHY STEIMLE, Department of Chemistry and Biochemistry, Arizona State University,
Tempe, AZ, USA.
The bonding and electrostatic properties of gold containing molecules are highly influenced by the large relativistic and
electron correlation effects.a Here we report on the electricpermanent dipole moment measurement and hyperfine interaction
analysis of the 2 ∆3/2 -2 Π3/2 and 2 ∆5/2 -2 Π3/2 bands of AuS. A cold molecular beam sample of gold sulfide was generated
using a supersonic laser ablation source. The electronic bands were recorded at high resolution (35 MHz, FWHM) using laser
excitation spectroscopy both field-free and in the presence of a static electric field. The observed hyperfine spectral features
were assigned and a set of spectroscopic parameters for the 2 ∆ and 2 Π states were obtained. The Stark induced shifts of
selected low-rotational features were analyzed to determine the permanent electric dipole moments in both the ground and
excited states.
a
P. Pyykko; Angew Chem. Int[43] , 4412,(2004).
RA08
10:46 – 11:01
HIGH-ACCURACY CALCULATION OF Cu ELECTRIC-FIELD GRADIENTS: A REVISION OF THE Cu NUCLEAR
QUADRUPOLE MOMENT VALUE
LAN CHENG, Department of Chemistry, The University of Texas, Austin, TX, USA; DEVIN A. MATTHEWS,
Department of Chemistry and Biochemistry, The University of Texas, Austin, TX, USA; JÜRGEN GAUSS, Institut
für Physikalische Chemie, Universität Mainz, Mainz, Germany; JOHN F. STANTON, Department of Chemistry,
The University of Texas, Austin, TX, USA.
A revision of the value for the Cu nuclear quadrupole moment (NQM) is reported based on high-accuracy ab initio
calculations on the Cu electric field gradients in the CuF and CuCl molecules. Electron-correlation effects have systematically
been taken into account using a hierarchy of coupled-cluster methods including up to quadruple excitations. It is shown
that the CCSD(T)Λ method provides a more reliable treatment of triples corrections for Cu electric-field gradients than the
ubiquitously applied CCSD(T) method, which is tentatively attributed to the importance of the wavefunction relaxation in the
calculations of a core property. Augmenting large-basis-set CCSD(T)Λ results with the remaining corrections obtained using
additive schemes, including full triples contributions, quadruples contributions, zero-point vibrational corrections, spin-orbit
corrections, as well as the correction from the Gaunt term, a new value of 209.7(50) mbarn for the Cu NQM has been obtained.
The new value substantially reduces the uncertainty of this parameter in comparison to the standard value of 220(15) mbarn
obtained from a previous muonic experiment.
163
RA09
11:03 – 11:18
+
CATION-π AND CH-π INTERACTIONS IN THE COORDINATION AND SOLVATION OF Cu (ACETYLENE)n (n=16) COMPLEXES INVESTIGATED VIA INFRARED PHOTODISSOCIATION SPECTROSCOPY
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ANTONIO DAVID BRATHWAITE, College of Science and Mathematics, University of the Virgin Islands, St.
Thomas, USVI; RICHARD S. WALTERS, TIMOTHY B WARD, MICHAEL A DUNCAN, Department of Chemistry, University of Georgia, Athens, GA, USA.
RA10
in
Mass-selected copper-acetylene cation complexes of the form Cu(C2 H2 )n + are produced by laser ablation and studied
via infrared laser photodissociation spectroscopy in the C-H stretching region (3000-3500 cm−1 ). Spectra for larger species
are measured via ligand elimination, whereas argon tagging is employed to enhance dissociation yields in smaller complexes.
The number of infrared active bands, their frequency positions and their relative intensities provide insight into the structure
and bonding of these ions. Density functional theory calculations are carried out in support of this work. The combined data
show that cation-π bonds are formed for the n=1-3 species, resulting in red-shifted C-H stretches on the acetylene ligands.
Three acetylene ligands complete the coordination of the copper cation. Additional ligands (n=4-6) solvate the n=3 core by
forming CH-pi bonds. Distinctive vibrational patterns are exhibited for coordinated vs. solvent ligands. Theory reproduces
these results.
ANION PHOTOELECTRON SPECTROSCOPIC STUDIES OF
BONYL COMPLEXES
NbCr(CO)−
n
11:20 – 11:35
(n = 2,3) HETEROBIMETALLIC CAR-
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MELISSA A. BAUDHUIN, PRAVEENKUMAR BOOPALACHANDRAN, DOREEN LEOPOLD, Chemistry
Department, University of Minnesota, Minneapolis, MN, USA.
−
Anion photoelectron spectra and density functional calculations are reported for NbCr(CO)−
2 and NbCr(CO)3 complexes
prepared by addition of Cr(CO)6 vapor to a flow tube equipped with a niobium cathode discharge source. Electron affinities
(± 0.007 eV) are measured to be 1.668 eV for NbCr(CO)2 and 1.162 eV for NbCr(CO)3 , values which exceed the 0.793
eV electron affinity previously measured for ligand-free NbCr. The vibrationally-resolved 488 nm photoelectron spectra
are compared with Franck-Condon spectra predicted for various possible isomers and spin states of the anionic and neutral
metal carbonyl complexes. Results are also compared with photoelectron spectra of the corresponding chromium carbonyl
complexes and of NbCr and NbCr− , which have formal bond orders of 5.5 (2 ∆) and 6 (1 Σ+ ), respectively. These comparisons
help to elucidate the effects of sequential carbonylation on this multiple metal-metal bond, and of the formation of this bond
on the chromium-carbonyl interactions.
RA11
11:37 – 11:52
MASS-ANALYZED THRESHOLD IONIZATION SPECTROSCOPY OF CYCLIC La(C5 H6 ) FORMED BY La ATOM
ACTIVATION OF PENTYNE AND PENTADIENE
WENJIN CAO, YUCHEN ZHANG, DONG-SHENG YANG, Department of Chemistry, University of Kentucky,
Lexington, KY, USA.
La atom reactions with 1-pentyne (CH≡CCH2 CH2 CH3 ) and 1,4-pentadiene (CH2 = CHCH2 CH = CH2 ) were carried
out in a laser-ablation molecular beam source. La(C5 H6 ) was observed in the two reactions through time-of-flight mass
spectrometry and characterized by mass-analyzed threshold ionization spectroscopy. The most stable isomer of La(C5 H6 )
was identified as a six-membered metallacycle, La(CH2 CH = CHCH = CH), with La binding to the two terminal carbon
atoms of the unsaturated hydrocarbon. The metallacycle is formed by hydrogen elimination and migration induced by the
La atom. The neutral complex with C1 symmetry has a doublet ground state, and the corresponding ion has a singlet state
generated by the removal of a La 6s-based electron. The adiabatic ionization energy of the metallacycle was determined to
be 37941 (5) cm−1 . Three vibrational modes of the ion were measured to be 318, 407, and 538 cm−1 , which correspond
to the La-ligand stretching, carbon skeleton bending with CH2 rocking, and carbon skeleton bending with CH2 twisting,
respectively. In addition, two hot bands were observed at 276 and 367 cm-1 below the origin band and identified to be
the vibrational frequencies of the La-ligand stretching and carbon skeleton bending with CH2 rocking modes of the neutral
complex.
164
RB. Mini-symposium: Accelerator-Based Spectroscopy
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Chair: Gert von Helden, Fritz Haber Institute - MPG, Berlin, Germany
RB01
INVITED TALK
8:30 – 9:00
PROBING INTRA- AND INTER- MOLECULAR INTERACTIONS VIA IRMPD EXPERIMENTS AND COMPUTATIONAL CHEMISTRY
in
SCOTT HOPKINS, TERRY McMAHON, Department of Chemistry, University of Waterloo, Waterloo, ON,
Canada.
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Experiments carried out at the CLIO Free Electron Facility have been used to probe a range of novel bonding motifs
and dissociation dynamics in a variety of chemical systems. Among these are species which exhibit anion-pi interactions in
complexes of halide ions with aromatic ring systems with electron withdrawing substituents; charge solvated and zwitterionic
clusters of protonated methylamines with phenylalanines; hydrogen bonded dimers of nucleic acid analogues and Pd complexes potentially involving agnostic hydrogen bond interactions. Accompanying DFT computational work is used to assist
in identifying the most probable structure(s) present in the IRMPD experiments.
RB02
9:05 – 9:20
EXPLORING CONFORMATION SELECTIVE FAR INFRARED ACTION SPECTROSCOPY OF ISOLATED
MOLECULES AND SOLVATED CLUSTERS
DANIËL BAKKER, ANOUK RIJS, FELIX Laboratory, Radboud University Nijmegen, Nijmegen, The Netherlands; JÉRÔME MAHÉ, MARIE-PIERRE GAIGEOT, Laboratoire Analyse et Modélisation pour la Biologie et
l’Environnement, Université d’Evry val d’Essonne, Evry, France.
Far-Infrared (IR) spectroscopy has been labeled as a promising method
for identifying structural motifs in large molecules. However, several hurdles
have kept this promising spectral region from breaking through to widespread
use for gas phase experiments. Normal modes in the far-IR mostly have
weak intensities, and high brightness sources of far-IR radiation are rare.
Moreover, standard density functional theory - applied to identify the specific molecular structure responsible for the measured IR spectra - does not
reproduce features in the far-IR well. This mismatch can be attributed to the
high degree of anharmonicity of many of the normal modes present in the farIR. We have overcome these hurdles by combining an advanced laser source
with novel experiments and high-level dynamical calculations.
We present far-IR spectra of a family of phenolic molecules and solvated
clusters, obtained using the free electron laser FELIX. By employing IR-UV ion-dip spectroscopy in the gas phase, we are
able to obtain conformer specific far-IR spectra of isolated molecules or solvated clusters. The studied systems display both
intra- and intermolecular hydrogen bonding, enabling us to study the merits of far-IR action spectroscopy for direct probing
of these weak interactions. Moreover, the combination of far-IR experiments with quantum chemical calculations allows
us to test the limits of the harmonic approximation in DFT calculations, and to test the possibilities of employing a more
sophisticated technique, namely Born-Oppenheimer molecular dynamics.
165
RB03
9:22 – 9:37
FIRST INFRARED PREDISSOCIATION SPECTRA OF He-TAGGED PROTONATED PRIMARY ALCOHOLS AT 4 K
ar
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ALEXANDER STOFFELSa , BRITTA REDLICH, J. OOMENS, Institute for Molecules and Materials (IMM),
Radboud University Nijmegen, Nijmegen, Netherlands; OSKAR ASVANY, SANDRA BRÜNKEN, PAVOL
JUSKO, SVEN THORWIRTH, STEPHAN SCHLEMMER, I. Physikalisches Institut, Universität zu Köln, Köln,
Germany.
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Cryogenic multipole ion traps have become popular devices in the development of sensitive action-spectroscopic techniques. The low ion temperature leads to enhanced spectral resolution, and less congested spectra. In the early 2000s, a
22-pole ion trap was coupled to the Free-Electron Laser for Infrared eXperiments (FELIX), yielding infrared Laser Induced
Reaction (LIR) spectra of the molecular ions C2 H2 + and CH5 +b . This pioneering work showed the great opportunities combining cold mass-selected molecular ions with widely tunable broadband IR radiation.
In the past year a cryogenic (T>3.9 K) 22-pole ion trap designed and built in Cologne (FELion) has been successfully
coupled to FELIX, which in its current configuration provides continuously tunable infrared radiation from 3 µm to 150 µm,
hence allowing to probe characteristic vibrational spectra in the so-called ”fingerprint region” with a sufficient spectral energy
density also allowing for multiple photon processes (IR-MPD). Here we present the first infrared predissociation spectra of
He-tagged protonated methanol and ethanol (MeOH2 + /EtOH2 + ) stored at 4 K. These vibrational spectra were recorded with
both a commercial OPO and FELIX, covering a total spectral range from 3700 cm−1 to 550 cm−1 at a spectral resolution of a
few cm−1 . The H-O-H stretching and bending modes clearly distinguish the protonated alcohols from their neutral analoga.
For EtOH2 + , also IR-MPD spectra of the bare ion could be recorded. The symmetric and antisymmetric H-O-H stretching
bands at around 3 µm show no significant shift within the given spectral resolution in comparison to those recorded with
He predissociation, indicating a rather small perturbation caused by the attached He. The vibrational bands were assigned
using quantum-chemical calculations on different levels of theory. The computed frequencies correspond favorably to the
experimental spectra. Subsequent high resolution measurements could lead to a better structural characterization of these
protonated alcohols.
a
b
also at: I.Physikalisches Institut, Universität zu Köln, Köln, Germany.
Asvany et al.: Phys. Rev.Lett. 94, 073001 (2005), Asvany et al.: Science 309, 1219-1222 (2005)
RB04
9:39 – 9:49
METAL ION INDUCED PAIRING OF CYTOSINE BASES: FORMATION OF I-MOTIF STRUCTURES IDENTIFIED BY
IR ION SPECTROSCOPY
JUEHAN GAO, GIEL BERDEN, J. OOMENS, Institute for Molecules and Materials (IMM), Radboud University Nijmegen, Nijmegen, Netherlands.
While the Watson-Crick structure of DNA is among the most well-known molecular structures of our time, alternative
base-pairing motifs are also known to occur, often depending on base sequence, pH, or presence of cations. Pairing of two
cytosine (C) bases induced by the sharing of a single proton (C-H+ -C) gives rise to the so-called i-motif, occurring particularly
in the telomeric region of DNA, and particularly at low pH. At physiological pH, silver cations were recently suggested to
form cytosine dimers in a C-Ag+ -C structure analogous to the hemiprotonated cytosine dimer, which was later confirmed by
IR spectroscopy.1 Here we investigate whether Ag+ is unique in this behavior.
Using infrared action spectroscopy employing the free-electron laser FELIX and a tandem mass spectrometer in combination with quantum-chemical computations, we investigate a series of C-M+ -C complexes, where M is Cu, Li and Na.
The complexes are formed by electrospray ionization (ESI) from a solution of cytosine and the metal chloride salt in acetonitrile/water. The complexes of interest are mass-isolated in the cell of a FT ion cyclotron resonance mass spectrometer, where
they are irradiated with the tunable IR radiation from FELIX in the 600 - 1800 cm−1 range. Spectra in the H-stretching range
are obtained with a LaserVision OPO.
Both experimental spectra as well as theoretical calculations indicate that while Cu behaves as Ag, the alkali metal ions
induce a clearly different dimer structure, in which the two cytosine units are parallelly displaced. In addition to coordination
to the ring nitrogen atom, the alkali metal ions coordinate to the carbonyl oxygen atoms of both cytosine bases, indicating
that the alkali metal ion coordination favorably competes with hydrogen bonding between the two cytosine sub-units of the
i-motif like structure.
1. Berdakin, Steinmetz, Maitre, Pino, J. Phys. Chem. A 2014, 118, 3804
166
RB05
9:51 – 10:06
MOLECULAR PROPERTIES OF THE ”ANTI-AROMATIC” SPECIES CYCLOPENTADIENONE, C5 H5 =0
ar
y
THOMAS ORMOND, BARNEY ELLISON, JOHN W DAILY, Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO, USA; JOHN F. STANTON, Department of Chemistry, The University of Texas,
Austin, TX, USA; MUSAHID AHMED, UXSL, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA; TIMOTHY S. ZWIER, Department of Chemistry, Purdue University, West Lafayette,
IN, USA; PATRICK HEMBERGER, General Energy, Paul Scherrer Institute, Villigen, Switzerland.
A common intermediate in the high temperature combustion of benzene is cyclopentadienone,
C5 H4 =O. Cyclopentadienone is considered to be an “anti-aromatic” molecule. It is certainly a
metastable species; samples persist at LN2 temperatures but dimerize upon warming to -80◦ C. It
+
is of great interest to physically characterize this “anti-aromatic” species. The microwave spectrum,
4 π electrons — "anti-aromatic"
the infrared spectrum, the ionization energy, and the electron affinity of cyclopentadienone have been
measured. Flash pyrolysis of o–phenylene sulfite (C6 H4 O2 SO) provides molecular beams of C5 H4 =O
entrained in a rare gas carrier. The beams are interrogated with time-of-flight photoionization mass spectrometry, confirming
the clean, intense production of C5 H4 =O. a) Chirped-pulse Fourier transform microwave spectroscopy and CCSD(T) electronic structure calculations have combined to determinea the re molecular structure of C5 H4 =O. b) Guided by CCSD(T)
electronic structure calculations, the matrix infrared absorbance spectrum of C5 H4 =O isolated in a 4 K neon matrix has been
usedb to assign 20 of the 24 fundamental vibrational frequencies. c) Imaging photoelectron photoion coincidence (iPEPICO)
spectrac of cyclopentadienone establishes the ionization energy, IE(C5 H4 =O), to be 9.41 ± 0.01 eV. d) Prof. A. Sanov’s
groupd has reported the electron affinity, EA(C5 H4 =O), to be 1.06 ± 0.01 eV.
O—
O
C
CH
HC
CH
HC
HC
CH
CH
in
C
HC
a
Kidwell et al. J. Phys. Chem. Letts. 2201 (2014)
Ormond et al. J. Phys. Chem. A 118, 708 (2014)
Ormond et al. Mol. Phys. in press (2015)
d
Khuseynov et al. J. Phys. Chem. A 118, 6965 (2014)
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b
c
Intermission
RB06
10:25 – 10:40
HIGH-RESOLUTION SYNCHROTRON INFRARED SPECTROSCOPY OF THIOPHOSGENE: THE ν1 , ν5 , 2ν4 , and ν2
+ 2ν6 bands
BOB McKELLAR, Steacie Laboratory, National Research Council of Canada, Ottawa, ON, Canada; BRANT
E BILLINGHURST, EFD, Canadian Light Source Inc., Saskatoon, Saskatchewan, Canada.
Thiophosgene (Cl2 CS) is a favorite model system for studies of photophysics, vibrational dynamics, and intersystem
interactions. But at high resolution its infrared spectrum is very congested due to hot bands and multiple isotopic species.
Previously, we reported the first high resolution IR study of this molecule, analyzing the ν2 (504 cm−1 ) and ν4 (471 cm−1 )
fundamental bands.a Here we continue, with analysis of the ν1 (1139 cm−1 ) and ν5 (820 cm−1 ) fundamentals for the two
most abundant isotopologues, 35 Cl2 CS and 35 Cl37 ClCS, based on spectra with a resolution of about 0.001 cm−1 obtained at
the Canadian Light Source far-infrared beamline using synchrotron radiation and a Bruker IFS125 Fourier transform spectrometer. The ν2 + ν4 (942 cm−1 ) and ν2 + 2ν6 (1104 cm−1 ) bands are also studied here. But so far the ν2 + ν6 combination
band (795 cm−1 ) resists analysis, as do the weak ν3 (292.9 cm−1 ) and ν6 (≈300? cm−1 ) fundamentals.
a
A.R.W. McKellar, B.E.Billinghurst, J. Mol. Spectrosc. 260, 66 (2010).
167
RB07
10:42 – 10:57
THE SOLEIL VIEW ON SULFUR OXIDES: THE S2 O BENDING MODE ν2 AT 380 cm
AN AUTOMATED SPECTRAL ASSIGNMENT PROCEDURE (ASAP)
−1
AND ITS ANALYSIS USING
ar
y
MARIE-ALINE MARTIN-DRUMEL, Spectroscopy Lab, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA; CHRISTIAN ENDRES, OLIVER ZINGSHEIM, T. SALOMON, I. Physikalisches Institut,
Universität zu Köln, Köln, Germany; JENNIFER VAN WIJNGAARDEN, Department of Chemistry, University
of Manitoba, Winnipeg, MB, Canada; OLIVIER PIRALI, SÉBASTIEN GRUET, AILES beamline, Synchrotron
SOLEIL, Saint Aubin, France; FRANK LEWEN, STEPHAN SCHLEMMER, I. Physikalisches Institut, Universität zu Köln, Köln, Germany; MICHAEL C McCARTHY, Atomic and Molecular Physics, Harvard-Smithsonian
Center for Astrophysics, Cambridge, MA, USA; SVEN THORWIRTH, I. Physikalisches Institut, Universität zu
Köln, Köln, Germany.
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The fundamental vibrational bending mode ν2 of disulfur monoxide, S2 O, and the associated hot band 2ν2 −ν2 have been
observed at high spectral resolution for the first time at the SOLEIL synchrotron facility using Fourier-transform far-infrared
spectroscopy. This transient species has been produced using a radio-frequency discharge by flowing SO2 over elemental
sulfur. The spectroscopic analysis has been performed using an Automated Spectral Assignment Procedure (ASAP) which
has enabled the accurate determination of more than 3500 energy levels of the v2 = 1 and v2 = 2 vibrational states. In
addition to the high-resolution synchrotron study, pure rotational spectra of S2 O in the v2 = 1 and 2 vibrational states were
observed in the frequency range 250 – 500 GHz in a long-path absorption cell.
RB08
THE SOLEIL VIEW ON SULFUR RICH OXIDES: THE ν3 MODE OF S2 O REVISITED
10:59 – 11:14
SVEN THORWIRTH, I. Physikalisches Institut, Universität zu Köln, Köln, Germany; MARIE-ALINE
CHRISTIAN ENDRES, OLIVER ZINGSHEIM, T. SALOMON, I. Physikalisches Institut, Universität zu Köln,
Köln, Germany; JENNIFER VAN WIJNGAARDEN, Department of Chemistry, University of Manitoba, Winnipeg, MB, Canada; OLIVIER PIRALI, SÉBASTIEN GRUET, AILES beamline, Synchrotron SOLEIL, Saint
Aubin, France; FRANK LEWEN, STEPHAN SCHLEMMER, I. Physikalisches Institut, Universität zu Köln,
Köln, Germany; MICHAEL C McCARTHY, Atomic and Molecular Physics, Harvard-Smithsonian Center for
Astrophysics, Cambridge, MA, USA.
In the course of our recent study of the ν2 bending mode of S2 O (Martin-Drumel el al.; see Talk P1190), the S-S
stretching mode ν3 located at 679cm−1 and first studied by Lindenmayer et al. in 1986 (J. Mol. Spectrosc. 119, 56) has
been re-investigated at the French national synchrotron facility SOLEIL using Fourier-transform far-infrared spectroscopy.
In addition to the vibrational fundamental, evidence for at least one more hot band, most likely ν3 + ν2 − ν2 , was found.
Complementary submillimeter wave measurements of the pure rotational spectrum in the v3 = 1 state were also performed.
168
RB09
11:16 – 11:31
−1
FT-IR MEASUREMENTS OF NH3 LINE INTENSITIES IN THE 60 – 550 CM
USING SOLEIL/AILES BEAMLINE
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KEEYOON SUNG, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, USA; SHANSHAN YU, Molecular Spectroscopy, Jet Propulsion Laboratory, Pasadena, CA, USA; JOHN PEARSON, Jet
Propulsion Laboratory, California Institute of Technology, Pasadena, CA, USA; LAURENT MANCERON,
Beamline AILES, Synchrotron SOLEIL, Saint-Aubin, France; F. KWABIA TCHANA, LISA, CNRS, Universités
Paris Est Créteil et Paris Diderot, Créteil, France; OLIVIER PIRALI, AILES beamline, Synchrotron SOLEIL,
Saint Aubin, France.
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Ammonia (NH3 ) has been found ubiquitous, e.g., in the interstellar medium, low-mass stars, Jovian planets of our solar
system, and possibly in the low temperature exoplanets. Their spectroscopic line parameters are essential in the accurate
interpretation of the planetary and astrophysical spectra observed with Herschel, SOFIA, ALMA, and JWST.
In our previous papera , the NH3 line positions in the far-IR region were studied for the ground state and ν2 in an
unprecedented accuracy, which revealed significant deficiencies in the NH3 intensities, for instance, some weak ∆K = 3 lines
were predicted to be 100 times stronger. Measurement of line intensity for these lines in a consistent manner is demanded
because the ∆K = 3 forbidden lines are only way other than collisions and l-doubled states to excite NH3 to K > 0 levels.
Recalling that NH3 transition lines in the high J and K up to 18 were detected toward the galactic center in the star forming
region of Sgr B2 , their accurate intensity measurements are critical in explaining the observed high K excitation, which will
provide insights into radiative-transfer vs. collision excitation mechanics of interstellar NH3 .
For this, we obtained a series of spectra of 14 NH3 in the 50 – 550 cm−1 using a Fourier-transform spectrometer, Bruker
125HR, and AILES beam line at Synchrotron SOLEIL, France. Line positions, intensities, and pressure-broadened halfwidths have been measured using non-linear least squares spectrum fitting algorithm. In this presentation we report and
discuss preliminary results of line position and intensity measurements for the inversion transitions in the ground state, ν2 ,
2ν2 , ν4 and for the vibration-rotation transitions of ν2 , 2ν2 , ν4 , 2ν2 − ν2 , ν4 − ν2 and ν4 − 2ν2 in this region. Comparison of
the new measurements with the current databases and ab initio calculations will be discussed.
a
S. Yu, et al. J. Chem. Phys. (2010) 174317/1-174317/14.
RB10
11:33 – 11:48
THE H2 O-CH3 F COMPLEX: A COMBINED MICROWAVE AND INFRARED SPECTROSCOPIC STUDY SUPPORTED
BY STRUCTURE CALCULATIONS
SHARON PRIYA GNANASEKAR, Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore, India; MANUEL GOUBET, Laboratoire PhLAM, Université de Lille 1, Villeneuve de Ascq,
France; ELANGANNAN ARUNAN, Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore, India; ROBERT GEORGES, IPR UMR6251, CNRS - Université Rennes 1, Rennes, France;
PASCALE SOULARD, PIERRE ASSELIN, MONARIS UMR8233, CNRS - UNiversité Paris 6 UPMC, Paris,
France; T. R. HUET, Laboratoire PhLAM, UMR8523 CNRS - Université Lille 1, Villeneuve d’Ascq, France;
OLIVIER PIRALI, AILES beamline, Synchrotron SOLEIL, Saint Aubin, France.
The H2 O-CH3 F complex could have two geometries, one with a hydrogen bond and one with the newly proposed carbon
bonda . While in general carbon bonds are weaker than hydrogen bonds, this complex appears to have comparable energies
for the two structures. Infrared (IR) and microwave (MW) spectroscopic measurements using, respectively, the Jet-AILES
apparatusb and the FTMW spectrometer at the PhLAM laboratoryc , have been carried out to determine the structure of
this complex. The IR spectrum shows the formation of the CH3 F- H2 O hydrogen bonded complex and small red-shifts in
OH frequency most probably due to (CH3 F)m -(H2 O)n clusters. Noticeably, addition of CH3 F in the mixture promotes the
formation of small water clusters. Preliminary MW spectroscopic measurements indicate the formation of the hydrogen
bonded complex. So far, we have no experimental evidence for the carbon bonded structure. However, calculations of the
Ar-CH3 F complex show three energetically equivalent structures: a T-shape, a “fluorine” bond and a carbon bond. The MW
spectrum of the (Ar)n -CH3 F complexes is currently under analysis.
a
Mani, D; Arunan, E. Phys. Chem. Chem. Phys. 2013, 15, 14377.
Cirtog, M; Asselin, P; Soulard, P; Tremblay, B; Madebene, B; Alikhani, M. E; Georges, R; Moudens, A; Goubet, M; Huet, T.R; Pirali, O; Roy, P. J. Phys. Chem. A. 2011,
115, 2523
c
Kassi, S; Petitprez, D; Wlodarczak, G. J. Mol. Struct. 2000, 517-518, 375
b
RC. Mini-symposium: Spectroscopy in the Classroom
169
Chair: Kristopher J Ooms, The King’s University, Edmonton, Alberta, Canada
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RC01
INVITED TALK
8:30 – 9:00
DIRECT DIGITAL SYNTHESIS CHIRPED PULSE MICROWAVE SPECTROMETERS FOR THE CLASSROOM AND
RESEARCH
GEOFFREY BLAKE, BRANDON CARROLL, IAN A FINNERAN, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA.
in
By combining the rapid development in direct digital synthesis circuitry and Field Programmable Gate Arrays (FPGAs)
coupled to fast A/D samplers, it is possible to construct high performance chirped pulse microwave spectrometers suitable for
gas-phase rotational spectroscopy experiments in undergraduate physical chemistry labs as well as graduate level research.
The technology is highly tailorable, and sufficiently robust that extensive experimentation is feasible in the teaching environment. The time domain nature of the experiment has strong ties to concepts in Nuclear Magnetic Resonance (NMR) widely
discussed in undergraduate curricula, and the software environment for the instrument control and spectral assignment can be
integrated with ab initio quantum chemistry predictions of molecular structure and dynamics.
RC02
9:05 – 9:20
A SIMPLE, COST EFFECTIVE RAMAN-FLUORESCENCE SPECTROMETER FOR USE IN LABORATORY AND
FIELD EXPERIMENTS
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FRANK E MARSHALL, MICHAEL A PRIDE, MICHELLLE ROJO, KATELYN R. BRINKER, ZACHARY
WALKER, Department of Chemistry, Missouri University of Science and Technology, Rolla, MO, USA;
MICHAEL STORRIE-LOMBARDI, Department of Physics, Harvey Mudd College and Kinohi Institute, Inc.,
Claremont, CA, USA; MELANIE R. MORMILE, Department of Biological Sciences, Missouri University of
Science and Technology, Rolla, MO, USA; G. S. GRUBBS II, Department of Chemistry, Missouri University of
Science and Technology, Rolla, MO, USA.
Research, design, construction, and operation of a portable mixed Raman and
Fluorescence type spectrometer implemented by the Missouri University of Science
and Technology’s Mars Rover Design Team will be presented. This spectrometer has
been built for the team’s annual competition. The spectrometer, completely built by
undergraduates, is designed to use a 50 mW, 532 nm constant waveform laser to probe
a sample of soil to find bacteria or bio-markers. However, initial tests of the spectrometer were carried out in a laboratory environment making the spectrometer also
suitable for simple undergraduate physical chemistry or chemical physics laboratory
experiments. The final cost of the device is roughly $2100, weighs 1.4 kg, and is 22.9
cm x 22.6 cm in size. Integrating the spectrometer with a computer database, results
from the competition, complications of fitting mixed Raman-Fluorescence spectra,
and future ideas/improvements will also be discussed.
RC03
9:22 – 9:37
LIF AND RAMAN SPECTROSCOPY IN UNDERGRADUATE LABS USING GREEN DIODE-PUMPED SOLID-STATE
LASERS
JEFFREY A. GRAY, Department of Chemistry, Ohio Northern University, Ada, OH, USA.
Electronic spectroscopy of molecular iodine vapor has long been studied in undergraduate physical chemistry teaching
laboratories, but the effectiveness of emission work has typically been limited by availability of instrumentation. This talk
shows how to make inexpensive green diode-pumped solid-state (DPSS) lasers easily tunable for efficient, selective excitation
of I2 . Miniature fiber-optic spectrometers then enable rotationally resolved fluorescence spectroscopy up to v” = 42 near 900
nm with acquisition times of less than one minute. DPSS lasers are also versatile excitation sources for vibrational Raman
spectroscopy, which is another common exercise that has been limited by lack of proper instrumentation in the teaching
laboratory. This talk shows how to construct a simple accessory for commercial fluorimeters to record vibrational Raman
spectra and depolarization ratios for CCl4 and C2 Cl4 as part of a lab exercise featuring molecular symmetry.
170
RC04
SPECFITTER: A LEARNING ENVIRONMENT FOR THE ROTATIONAL SPECTROSCOPIST
9:39 – 9:54
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YOON JEONG CHOI, WEIXIN WU, Natural and Social Science, Purchase College SUNY, Purchase, NY, USA;
A. J. MINEI, Department of Chemistry and Biochemistry, Division of Natural Sciences, College of Mount Saint
Vincent, Riverdale, NY, USA; S. A. COOKE, Natural and Social Science, Purchase College SUNY, Purchase, NY,
USA.
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A windows based, mouse-event driven software program
that acts a graphical user interface to Pickett’s fitting programs
has been created and improved. The program, SpecFitter, is
aimed at walking users through the process of assigning pure
rotational spectra. Rotational spectra, in XY format, may be
viewed and inspected and the user is provided with tools for observing and recording repeating, similar patterns of transitions.
The structure of these patterns is interpreted into “guesses” at
rotational constants which the user may then use to predict a
spectrum. Observed transition frequencies may then be assigned
quantum number transitions and appended to the .lin file through
mouse clicks. Although the thrust of this project is to develop
a users ability to assign spectra without knowing the molecule
producing the spectra the program can also read in and display
calculated structures of target molecules produced by the Gaussian03/09 software, or alternatively the user can draw their
own structures. Structures can be edited allowing users to observe the relationship between molecular structure and (i) the
direction of dipole moment components and (ii) the relationships between structure and rotational constants. Users may also
easily predict spectra from the molecules structure and further relate rotational constants to observed spectra. Students in
CHEM 3510 at Purchase College have been vital in developing the software.
RC05
9:56 – 10:11
APPLICATIONS OF GROUP THEORY: INFRARED AND RAMAN SPECTRA OF THE ISOMERS OF cis- AND trans1,2-DICHLOROETHYLENE
NORMAN C. CRAIG, Department of Chemistry and Biochemistry, Oberlin College, Oberlin, OH, USA.
A study of the vibrational spectra of cis- and trans-1,2-dichloroethylene provides an excellent way for undergraduates
to gain experience with the application of group theory in the physical chemistry laboratory. Although the group vibrations
are similar for these two molecules, the selection rules for infrared (IR) and Raman spectra differ significantly. Most of the
transitions for the fundamentals of the cis isomer of C2v symmetry are both IR and Raman active. Mutual exclusion for the
vibrational transitions applies to the centrosymmetric trans isomer of C2h symmetry. Thus, half the transitions for the trans
isomer are IR active and half are Raman active. The two isomers are volatile enough that gas-phase IR spectra can be recorded
at room temperature. Band shapes in gas-phase IR spectra provide additional evidence for assignments of fundamentals. The
two isomers are small enough that good quality quantum chemical calculations of harmonic frequencies can be done by
students with commercial software.
Intermission
171
RC06
10:30 – 10:40
INFRARED ANALYSIS OF COMBUSTION PRODUCTS AND INTERMEDIATES OF HYDROCARBON COMBUSTION FOR SEVERAL SPECIES
ar
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ALLEN WHITE, Department of Mechanical Engineering, Rose-Hulman Institute of Technology, Terre Haute,
IN, USA; REBECCA DEVASHER, Department of Chemistry, Rose-Hulman Institute of Technology, Terre Haute,
IN, USA.
in
Hydrocarbons, especially large ones such as isooctane, have infrared active species that give insight into combustion
stoichiometry and temperature. Here a Fourier-transform infrared spectrometer is utilized to study the IR active species for a
number of stociometric conditions for several fuels including isooctane, kerosene, and ethanol. Special attention is given to
intermediate species in different flame regions.
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RC07
10:42 – 10:52
CHIRPED-PULSE MICROWAVE SPECTROSCOPY IN THE UNDERGRADUATE CHEMISTRY CURRICULUM
SYDNEY A GASTER, TAYLOR M HALL, SEAN ARNOLD, GORDON G BROWN, Department of Science
and Mathematics, Coker College, Hartsville, SC, USA.
The use of chirped-pulse Fourier transform microwave (CP-FTMW) spectroscopy as a tool for training undergraduates
will be discussed. Coker College’s inexpensive, versatile CP-FTMW spectrometer has been applied both in the undergraduate
teaching laboratory and the undergraduate research laboratory. In both cases, the education of the students is a central priority
of the project. The study of 3-iodopyridine, a project recently completed by Coker undergraduate students, will be discussed.
Details of the Coker CP-FTMW spectrometer will also be presented.
RC08
10:54 – 11:04
USB SPECTROMETERS AND THE TEMPERATURE OF THE SUN: MEASURING BLACK BODY RADIATION IN
THE PALM OF YOUR HAND
DANIEL P. ZALESKI, BENJAMIN R HORROCKS, NICK WALKER, School of Chemistry, Newcastle University, Newcastle-upon-Tyne, United Kingdom.
A new experiment appropriate for both general chemistry and physical chemistry students will be described. The experiment utilizes ”pocket size” USB spectrometers (operating in the UV/vis region) coupled with fiber optic cables to record a
solar spectrum. A further extension of the experiment involves recording spectra of a light bulb at several voltages (and thus
resistances). Using provided software, students can fit black body distributions to their obtained spectra. The software will
display the acquired spectrum, a simulation based on their guess temperature, a simulation based on their fit, and OMC2 for
both. Students can then compare their results to the known temperature of the sun and the known temperature vs resistance
curve of tungsten.
172
RC09
11:06 – 11:16
13
VIBRATION-ROTATION ANALYSIS OF THE CO2 ASYMMETRIC STRETCH FUNDAMENTAL BAND IN AMBIENT AIR FOR THE PHYSICAL CHEMISTRY TEACHING LABORATORY
ar
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DAVID A DOLSON, CATHERINE B ANDERSa , Department of Chemistry, Wright State University, Dayton,
OH, USA.
a
in
The CO2 asymmetric stretch fundamental band near 4.3 µm is one of the strongest infrared absorption transitions of
all small molecules. This band is an undesired interference in most infrared spectra, but it also serves as a potential choice
for a vibration-rotation analysis experiment in the physical chemistry teaching laboratory. Due to the strength of this band
and the 1.1% natural abundance of carbon-13, the asymmetric stretch fundamental band of 13 CO2 is readily observable in
a typical ambient air background spectrum and is shifted sufficiently from the stronger 12 CO2 fundamental such that the
13
CO2 P-branch lines are almost completely free of interferences and are easily assigned. All of the 13 CO2 R-branch lines
appear within the 12 CO2 P-branch, which creates assignment challenges. Students in our program have analyzed the 13 CO2
fundamental asymmetric stretch band over a two-year period. Analyses of the P-branch line positions enabled the prediction
of additional R-branch line positions, which guided line identification and measurements in the 13 CO2 R-branch. C=O bond
lengths determined from analyses of the 13 CO2 spectra improved when R-branch lines were added to the initial P-branch
data sets. Spectral appearance, analyses and results will be presented for spectra obtained at 0.5 cm−1 resolution and at 0.125
cm−1 resolution. The challenge of predicting and finding the 13 CO2 R-branch lines among other interfering lines adds an
element of realism to this experiment that is not found in many student experiments of this type.
present address: Department of Biomolecular Sciences, Boise State University, Boise, ID, USA
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RC10
UTILIZING SPECTROSCOPIC RESEARCH TOOLS AND SOFTWARE IN THE CLASSROOM
11:18 – 11:33
G. S. GRUBBS II, Department of Chemistry, Missouri University of Science and Technology, Rolla, MO, USA.
Given today’s technological age, it has become crucial to be able to reach the student in a more ”tech-savvy” way
than traditional classroom methods afford. Given this, there are already a vast range of software packages available to the
molecular spectroscopist that can easily be introduced to the classroom with success. This talk will highlight taking a few
of these tools (Gaussian09, SPFIT/SPCAT, the AABS Package, LabViewTM , etc.) and implementing them in the classroom
to teach subjects such as Quantum Mechanics and Thermodynamics as well as to aid in the linkage between these subjects.
Examples of project implementation on both undergraduate and graduate level students will be presented with a discussion
on the successes and failures of such attempts.
173
RD. Astronomy
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y
Chair: Brett A. McGuire, California Institute of Technology, Pasadena, CA, USA
8:30 – 8:40
in
RD01
NEW INSTRUMENTAL TOOLS FOR ADVANCED ASTROCHEMICAL APPLICATIONS
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AMANDA STEBER, The Centre for Ultrafast Imaging (CUI), Universität Hamburg, Hamburg, Germany; SABRINA ZINN, MELANIE SCHNELL, CoCoMol, Max-Planck-Institut für Struktur und Dynamik der Materie,
Hamburg, Germany; ANOUK RIJS, Institute for Molecules and Materials (IMM), Radboud University Nijmegen,
Nijmegen, Netherlands.
Astrochemistry has been a growing field over the past several years. As the data from the Atacama Large Millimeter
Array (ALMA) becomes publicly available, new and fast techniques for the analysis of the data will need to be developed, as
well as fast, sensitive laboratory techniques. This lab is in the process of building up instrumentation that will be dedicated
to the measurement of astrochemically relevant species, both in the microwave and the millimeter wave regimes. Discharge
experiments, laser ablation experiments, as well as time of flight measurements will be possible with this instrumentation.
Coupled with instrumentation capabilities will be new software aimed at a speeding up the analysis. The laboratory data will
be used to search for new molecular signatures in the interstellar medium (ISM), and help to elucidate molecular reaction
pathways occurring in the ISM.
RD02
8:42 – 8:57
DOPPLER AND SUB-DOPPLER MILLIMETER AND SUB-MILLIMETER WAVE SPECTROSCOPY OF KEY ASTRONOMICAL MOLECULES: HNC AND CS
OLIVER ZINGSHEIM, THOMAS SCHMITT, FRANK LEWEN, STEPHAN
SVEN THORWIRTH, I. Physikalisches Institut, Universität zu Köln, Köln, Germany.
SCHLEMMER,
In the course of ongoing efforts to determine accurate pure rotational transition frequencies for the astronomical community, the millimeter- and submillimeter-wave spectra of HNC and selected isotopic species have been investigated using a
radio-frequency discharge of (isotopically enriched) methyl cyanide. Besides the ground vibrational state, vibrational satellites from the first excited bending mode were targeted. In part, rotational transitions were observed employing the Lamb-Dip
technique to obtain sub-Doppler resolution. The Lamb-dip technique has also been applied to other short-lived molecules
such as carbon monosulfide, CS.
174
RD03
MILLIMETRE-WAVE SPECTRUM OF ISOTOPOLOGUES OF ETHANOL FOR RADIO ASTRONOMY
8:59 – 9:14
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ADAM WALTERS, IRAP, Université de Toulouse 3 - CNRS - OMP, Toulouse, France; MIRKO SCHÄFER,
MATTHIAS H. ORDU, FRANK LEWEN, STEPHAN SCHLEMMER, HOLGER S. P. MÜLLER, I. Physikalisches Institut, Universität zu Köln, Köln, Germany.
a
Bouchez et al, JQSRT 113 (11), pp. 1148-1154, 2012.
Belloche et al. A&A 559, id.A47, 187pp., 2013.
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Complex molecules have been identified in star-forming regions and their formation is linked to the specific physical and
chemical conditions there. They are suspected to form a role in the origins of life. Amongst these, ethanol is a fairly abundant
molecule in warmer regions.
For this reason, we have recently carried out laboratory measurements and analyses of the rotational spectra of the
three mono-substituted deuterium isotopologues of ethanol (one of which, CH2 DCH2 OH, exists as two distinct conformers
according to the position of the deuterium atom with respect to the molecular skeleton). Measurements were taken between
35-500 GHz, allowing accurate predictions in the range of radio telescopes. We have concentrated on the lowest energy anti
conformers. The dataset was constrained for fitting with a standard Watson-S reduction Hamiltonian by rejecting transitions
from high-lying states, which appear to be perturbed by the gauche states, and by averaging some small methyl torsional
splits. This treatment is compatible with the needs for a first search in the interstellar medium, in particular in spectra
taken by ALMA. For this purpose an appropriate set of predictions will be included on the Cologne Database for Molecular
Spectroscopy.
Previous results on the two mono-substituted 13 C isotopologuesa which led to a tentative detection in Sgr B2(N)b will be
briefly summarized and compared with the latest measurements.
The usefulness of studying different isotopologues in the interstellar medium will also be rapidly addressed.
RD04
TERAHERTZ SPECTROSCOPY OF DEUTERATED METHYLENE BI-RADICAL, CD2
9:16 – 9:31
HIROYUKI OZEKI, Department of Environmental Science, Toho University, Funabashi, Japan;
STEPHANE BAILLEUX, Laboratoire PhLAM, Université de Lille - Sciences et Technologies, Villeneuve
d’Ascq, France.
Methylene, the parent of the carbene compounds, plays a crucial role in many chemical reactions. This bi-radical is a
known interstellar molecule that has been detected towards hot cores in dense interstellar clouds. CH2 is also thought to be
present in cometary atmospheres. In the gas phase chemical models of both dense and diffuse molecular clouds, CH2 is a key
intermediate in interstellar carbon chemistry which is produced primarily by dissociative recombination of the methyl ion,
+
CH+
3 . Recently tentative detection of the mono-deuterated methyl ion, CH2 D has been reported toward an infrared source
in the vicinity of Orion.a Deuterated methylene CHD and CD2 can be produced from this ion or its counterpart CHD+
2 by
dissociative recombination with an electron:
CH2 D+ + e− → CHD + H or CH2 + D,
(1)
−
CHD+
2 + e → CHD + D or CD2 + H.
(2)
Thus, both CHD and CD2 can be observed in warm interstellar clouds, where the deuterium fractionation process is important.
Precise laboratory reference data are desirable for radioastronomical observation of these molecules.
Here we report on our high-resolution spectroscopic investigation on the deuterated methylene radical, CD2 (X 3 B1 ) up
to 1.45 THz. At present time, eleven out of the twelve fine-structure components of four pure rotational transitions have been
newly recorded, and these measurements double the number of previously observed transitions.b CD2 was generated in a
discharge in CD2 CO which was obtained from the flash pyrolysis of acetic anhydride-d6 ((CD3 CO)2 O). Effort is currently
made to measure the astronomically important 111 − 000 transition whose fine-structure components are predicted to occur at
1.224,1.228 and 1.234 THz.
a
b
D. C. Lis, P. F. Goldsmith, E. A. Bergin et al. 2009, in Submillimeter Astrophysics and Technology, ASP Conf. Ser., 417, 23.
H. Ozeki and S. Saito J. Chem. Phys. 1996, 104, 2167.
175
RD05
9:33 – 9:48
+
THZ SPECTROSCOPY OF D2 H
SHANSHAN YU, JOHN PEARSON, TAKAYOSHI AMANO, Jet Propulsion Laboratory, California Institute
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Pure rotational transitions of D2 H+ observed by high-resolution spectroscopy have been limited so far to the J = 110 -101
transition at 691.7 GHz,a J = 220 −211 at 1.370 THz, and J = 111 −000 at 1.477 THz.bc As this ion is a light asymmetric-top
molecule, spectroscopic characterization and prediction of other rotational transition frequencies are not straightforward.
In this presentation, we extended the measurements up to 2 THz by using the JPL frequency multiplier chains, and
observed three new THz lines and re-measured the three known transitions. D2 H+ was generated in an extended negative
glow discharge cell cooled to liquid nitrogen temperature. Six rotational transition frequencies together with the combination
differences derived from three fundamental bands were subject to least square analysis to determine the molecular constants.
New THz measurements are definitely useful for better characterization of spectroscopic properties. The improved molecular
constants provide better predictions of other unobserved rotational transitions.
a
T. Hirao and T. Amano, Ap. J.,597, L85 (2003)
K. M. Evenson et al cited by O. L. Polyansky and A. R. W. McKellar, J. Chem. Phys., 92, 4039 (1990)
c
O. Asvany et al, Phys. Rev. Lett., 100, 233004 (2008)
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b
RD06
THZ SPECTROSCOPY OF
12
+ 13
CH ,
+
CH , AND
12
9:50 – 10:05
+
CD
SHANSHAN YU, BRIAN DROUIN, JOHN PEARSON, TAKAYOSHI AMANO, Jet Propulsion Laboratory,
California Institute of Technology, Pasadena, CA, USA.
In 1937, Dunhama detected a couple of unidentified lines in near-UV, and later Douglas and Herzbergb identified them
based on their laboratory observations to be low-J electronic transitions of CH+ . The electronic spectra, in particular the
A1 Π − X 1 Σ+ band, have been investigated extensively. On the other hand, the pure rotational transitions have not been
studied so extensively. Only the lowest rotational transition, J = 1 − 0, was observed in the laboratory for the normal species,
13
CH+ , and CD+ .cd
Based on the laboratory frequency, CH+ was detected in star forming regions with the Hershel space observatory. Cernicharo et al identified pure rotational transitions from J = 2 − 1 to J = 6 − 5 in the far-infrared region in the ISO spectrum
of the planetary nebula NGC 7027e . The ISO spectra, however, were of low-resolution, so high-resolution spectroscopic
observation is highly desirable.
In this presentation, we have extended the measurements to higher-J lines up to 2 THz. For production of CH+ , an
extended negative glow discharge in a gas mixture of CH4 (∼ 0.5 mTorr) diluted in He (∼ 60 mTorr) was used. The optimum
discharge current was about 15 mA and the axial magnetic filed to 160 Gauss was applied up. The discharge cell was cooled
down to liquid nitrogen temperature. Several frequency multiplier chains, developed at JPL and purchased from Virginia
Diodes, were used as THz radiation sources.
New THz measurements are not only useful for providing better characterization of spectroscopic properties but also will
serve as starting point for astronomical observations.
a
T. Dunham, Publ. Astron. Soc. Pac., 49, 26 (1937)
A. E. Douglas and G. Herzberg, Ap. J. 94, 381 (1941)
c
T. Amano, Ap.J.Lett., 716, L1 (2010)
d
T. Amano, J. Chem. Phys., 133, 244305 (2010)
e
J. Cernicharo et al., Ap. J. Lett., 483, L65 (1997)
b
176
RD07
10:07 – 10:22
+
+
ROTATIONAL SPECTROSCOPY OF VIBRATIONALLY EXCITED N2 H and N2 D UP TO 2 THZ
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y
SHANSHAN YU, JOHN PEARSON, BRIAN DROUIN, TIMOTHY J CRAWFORD, ADAM M DALY, BEN
ELLIOTT, TAKAYOSHI AMANO, Jet Propulsion Laboratory, California Institute of Technology, Pasadena,
CA, USA.
Terahertz absorption spectroscopy was employed to extend the measurements on the pure rotational transitions of N2 H+ ,
N2 D+ and their 15 N-containing isotopologues in the ground state and first excited vibrational states for the three fundamental
vibrational modes. In total 88 new pure rotational transitions were observed in the range of 0.7–2.0 THz. The observed
transition frequencies were fit to experimental accuracy, and the improved molecular parameters were obtained. The new
measurements and predictions will support the analysis of high-resolution astronomical observations made with facilities
such as SOFIA and ALMA where laboratory rest frequencies with uncertainties of 1 MHz or smaller are required for proper
analysis of velocity resolved astrophysical components.
RD08
35
+
in
Intermission
37
10:41 – 10:56
+
NEW ACCURATE WAVENUMBERS OF H Cl AND H Cl ROVIBRATIONAL TRANSITIONS IN THE v = 0 − 1
BAND OF THE 2 Π STATE.
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JOSE LUIS DOMENECH, MAITE CUETO, VICTOR JOSE HERRERO, ISABEL TANARRO, Molecular
Physics, Instituto de Estructura de la Materia (IEM-CSIC), Madrid, Spain; JOSE CERNICHARO, Molecular
Astrophysics, ICMM, Madrid, Spain.
HCl+ is a key intermediate in the interstellar chemistry of chlorine. It has been recently identified in space from Herschel’s spectraa and it has also been detected in the laboratory through its optical emissionb , infraredc and mm-wave spectrad .
Now that Hershchel is decomissioned, further astrophysical studies on this radical ion will likely rely on ground-based observations in the mid-infrared. We have used a difference frequency laser spectrometer coupled to a hollow cathode discharge
to measure the absorption spectrum of H35 Cl+ and H37 Cl+ in the v = 0 − 1 band of the 2 Π state with Dopppler limited
resolution. The accuracy of the individual measurements (∼ 10 MHz (3σ)) relies on a solid state wavemeter referenced to an
iodine-stabilized Ar+ laser.
a
M. De Luca et al., Astrophys. J. Lett. 751, L37 (2012)
W. D. Sheasley and C. W. Mathews, J. Mol. Spectrosc. 47, 420 (1973)
c
P. B. Davies, P. A. Hamilton, B. A. Johnson, Mol. Phys. 57, 217 (1986)
d
H. Gupta, B. J. Drouin, and J. C. Pearson, Astrophys. J. Lett. 751, L37 (2012)
b
RD09
10:58 – 11:13
OSCILLATOR STRENGTHS AND PREDISSOCIATION RATES FOR W − X BANDS AND THE 4P5P COMPLEX IN
13 18
C O
MICHELE EIDELSBERG, JEAN LOUIS LEMAIRE, Meudon, Observatoire de Paris, Paris, France;
STEVEN FEDERMAN, Physics and Astronomy, University of Toledo, Toledo, OH, USA; GLENN STARK, Department of Physics, Wellesley College, Wellesley, MA, USA; ALAN HEAYS, Leiden Observatory, University of
Leiden, Leiden, Netherlands; LISSETH GAVILAN, Institut d’Astrophysique Spatiale, Campus de l’Université
Paris XI, Orsay, France; JAMES R LYONS, School of Earth and Space Exploration, Arizona State University, Tempe, AZ, USA; PETER L SMITH, 93 Pleasant St., 93 Pleasant St., Watertown, MA, USA; NELSON DE
OLIVEIRA, DENIS JOYEUX, DESIRS Beamline, Synchrotron SOLEIL, Saint Aubin, France.
In our ongoing experiments on the DESIRS beam-line at the SOLEIL Synchrotron, we are acquiring the necessary data
on oscillator strengths and predissociation rates for modeling CO photochemistry in astronomical environments. A VUV
Fourier Transform Spectrometer with a resolving power of about 350,000 allows us to discern individual lines in electronic
transitions. Here we focus on results obtained from absorption spectra of 13 C18 O, for the W 1 Π − X 1 Σ+ bands with
v ′ = 0, 2, and 3 and v ′′ = 0 and three resolved bands involving transitions to the upper levels 4pπ(2), 5pπ(0), and 5pσ(0) of
the 4p(2) and 5p(0) complexes. We compare our results with earlier determinations for this isotopologue of CO, as well as
with our SOLEIL measurements on 12 C16 O, 13 C16 O, and 12 C18 O.
177
RD10
11:15 – 11:30
2
LINE STRENGTHS OF ROVIBRATIONAL AND ROTATIONAL TRANSITIONS IN THE X Π GROUND STATE OF OH
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JAMES S.A. BROOKE, Department of Chemistry, University of York, York, United Kingdom;
PETER F. BERNATH, Department of Chemistry and Biochemistry, Old Dominion University, Norfolk, VA, USA;
COLIN WESTERN, School of Chemistry, University of Bristol, Bristol, United Kingdom; CHRIS SNEDEN,
Department of Astronomy, The University of Texas at Austin, Austin, TX, USA; GANG LI, IOULI E GORDON,
Atomic and Molecular Physics, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA.
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For cool stellar and substellar objects including brown dwarfs and exoplanets, atomic lines weaken and detailed elemental and isotopic abundances are often derived from molecular absorption features. We have embarked on a project to
provide molecular line lists based on combining experimental observations for line positions and ab initio calculations for
line strengths. In this talk we present a new line list including positions and absolute intensities (in the form of Einstein
A values and oscillator strengths) that has been produced for the OH ground X2 Π state rovibrational (Meinel system) and
pure rotational transitions. All possible allowed transitions are included with v up to 13, and J up to between 9.5 and 59.5,
depending on the band. A new fit to determine molecular constants has been performed, based on the fit of Bernath and
Colin [J. Mol. Spectrosc. 257, 20 (2009)], but includes some new rotational data and a simultaneous fitting of all molecular
constants. The line intensities are based on a new dipole moment function, which is a combination of two high level ab initio
calculations. The calculations show good agreement with an experimental v=1 lifetime, experimental dipole moment values
and ∆v=2 line intensity ratios from an observed laboratory spectrum. A new partition function was computed suitable for
use up to about 6000 K. The new line list was also evaluated by determining the oxygen abundance for a number of cool stars
from high resolution observations in the near infrared region.
RD11
CLASS I METHANOL MASER CONDITIONS NEAR SNRS
11:32 – 11:42
BRIDGET C. McEWEN, YLVA M. PIHLSTRÖM, Physics and Astronomy, The University of New Mexico, Albuquerque, NM, USA; LORÁNT O. SJOUWERMAN, NRAO, NRAO, Socorro, NM, USA.
We present results from calculations of the physical conditions necessary for the occurrence of 36.169 (4−1 − 30 E),
44.070 (70 − 61 A+ ), 84.521 (5−1 − 40 E), and 95.169 (80 − 71 A+ ) GHz methanol (CH3 OH) maser emission lines near
supernova remnants (SNRs), using the MOLPOP-CEP program. The calculations show that given a sufficient methanol
abundance, methanol maser emission arises over a wide range of densities and temperatures, with optimal conditions at
n ∼ 104 − 106 cm−3 and T > 60 K. The 36 GHz and 44 GHz transitions display more significant maser optical depths
compared to the 84 GHz and 95 GHz transitions over the majority of physical conditions. It is also shown that line ratios are
an important and applicable probe of the gas conditions. The line ratio changes are largely a result of the E-type transitions
becoming quenched faster at increasing densities. The modeling results will be discussed using recent observations of CH3 OH
masers near the SNRs G1.4−0.1, W28, and Sgr A East and used as a diagnostic tool to estimate densities and temperatures of
the regions in which the CH3 OH masers are observed.
178
RD12
11:44 – 11:59
THE MISSING LINK: ROTATIONAL SPECTRUM AND GEOMETRICAL STRUCTURE OF DISILICON CARBIDE,
Si2 C
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y
Cambridge, MA, USA; JOSHUA H BARABAN, Department of Chemistry, University of Colorado, Boulder,
CO, USA; BRYAN CHANGALA, JILA, National Institute of Standards and Technology and Univ. of Colorado Department of Physics, University of Colorado, Boulder, CO, USA; JOHN F. STANTON, Department of
Chemistry, The University of Texas, Austin, TX, USA; MARIE-ALINE MARTIN-DRUMEL, Spectroscopy Lab,
Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA; SVEN THORWIRTH, I. Physikalisches
Institut, Universität zu Köln, Köln, Germany; NEIL J REILLY, Department of Chemistry, Marquette University,
Milwaukee, WI, USA; CARL A GOTTLIEB, Radio and Geoastronomy Division, Harvard-Smithsonian Center
for Astrophysics, Cambridge, MA, USA.
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Disilicon carbide Si2 C is one of the most fascinating small molecules for both fundamental and applied reasons. Like
C3 , it has a shallow bending angle, and may therefore also serve as a classic example of a quasilinear species. Si2 C is also
thought to be quite stable. Mass spectrometric studies conclude that it is one of the most common gas-phase fragments in the
evaporation of silicon carbide at high temperature. For these same reasons, it may be abundant in certain evolved carbon stars
such as IRC+12016. Its electronic spectrum was recently studied by several of us, but its ground state geometry and rotational
spectrum remain unknown until now. Using sensitive microwave techniques and high-level coupled cluster calculations, Si2 C
has been detected in the radio band, and is found to be highly abundant. Its more common rare isotopic species have also be
observed either in natural abundance or using isotopically-enriched samples, from which a highly precise semi-experimental
structure has been derived. This talk will summarize recent work, and discuss the prospects for astronomical detection. Now
that all four of the Sim Cn clusters with m + n = 3 has been detected experimentally, a rigorous comparison of their structure
and chemical bonding can be made.
RE. Instrument/Technique Demonstration
179
Chair: Arthur Suits, Wayne State University, Detroit, MI, USA
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RE01
8:30 – 8:45
OPTIMIZATION OF EXTREME ULTRAVIOLET LIGHT SOURCE FROM HIGH HARMONIC GENERATION FOR
CONDENSED-PHASE CORE-LEVEL SPECTROSCOPY
MING-FU LIN, MAX A VERKAMP, ELIZABETH S RYLAND, KRISTIN BENKE, KAILI ZHANG,
MICHAELA CARLSON, JOSH VURA-WEIS, Department of Chemistry, University of Illinois at UrbanaChampaign, Urbana, IL, USA.
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Extreme ultraviolet (XUV) light source from high-order harmonic generation has been shown to be a powerful tool for
core-level spectroscopy. In addition, this light source provides very high temporal resolution (10−18 s to 10−15 s) for timeresolved transient absorption spectroscopy. Most applications of the light source have been limited to the studies of atomic
and molecular systems, with technique development focused on optimizing for shorter pulses (i.e. tens of attoseconds) or
higher XUV energy (i.e. keV range). For the application to general molecular systems in solid and liquid forms, however, the
XUV photon flux and stability are highly demanded due to the strong absorption by substrates and solvents. In this case, the
main limitation is due to the stability of the high order generation process and the limited bandwidth of the XUV source that
gives only discrete even/odd order peaks. Consequently, this results in harmonic artifact noise that overlaps with the resonant
signal. In our current study, we utilize a semi-infinite cell for high harmonic generation from two quantum trajectories (i.e.
short and long) at over-driven NIR power. This condition, produces broad XUV spectrum without using complicated optics
(e.g. hollow-core fibers and double optical gating). This light source allows us to measure the static absorption spectrum
of the iron M-edge from a Fe(acac)3 molecular solid film, which shows a resonant feature of 0.01 OD ( 2.3% absorption).
Moreover, we also investigate how sample roughness affects the static absorption spectrum. We are able to make smooth solar
cell precursor materials (i.e. PbI2 and PbBr2 ) by spin casting and observe iodine (50 eV) and bromine (70 eV) absorption
edges in the order of 0.05 OD with minimal harmonic artifact noise.
RE02
8:47 – 9:02
DEVELOPMENT OF TWO-PHOTON PUMP POLARIZATION SPECTROSCOPY PROBE TECHNIQUE (TPP-PSP) FOR
MEASUREMENTS OF ATOMIC HYDROGEN .
AMAN SATIJA, ROBERT P. LUCHT, Mechanical Engineering, Purdue University, West Lafayette, IN, USA.
Atomic hydrogen (H) is a key radical in combustion and plasmas. Accurate knowledge of its concentration can be
used to better understand transient phenomenon such as ignition and extinction in combustion environments. Laser induced
polarization spectroscopy is a spatially resolved absorption technique which we have adapted for quantitative measurements
of H atom. This adaptation is called two-photon pump, polarization spectroscopy probe technique (TPP-PSP) and it has been
implemented using two different laser excitation schemes. The first scheme involves the two-photon excitation of 1S-2S
transitions using a linearly polarized 243-nm beam. An anisotropy is created amongst Zeeman states in 2S-3P levels using a
circularly polarized 656-nm pump beam. This anisotropy rotates the polarization of a weak, linearly polarized probe beam
at 656 nm. As a result, the weak probe beam “leaks” past an analyzer in the detection channel and is measured using a
PMT. This signal can be related to H atom density in the probe volume. The laser beams were created by optical parametric
generation followed by multiple pulse dye amplification stages. This resulted in narrow linewidth beams which could be
scanned in frequency domain and varied in energy. This allowed us to systematically investigate saturation and Stark effect
in 2S-3P transitions with the goal of developing a quantitative H atom measurement technique. The second scheme involves
the two-photon excitation of 1S-2S transitions using a linearly polarized 243-nm beam. An anisotropy is created amongst
Zeeman states in 2S-4P transitions using a circularly polarized 486-nm pump beam. This anisotropy rotates the polarization
of a weak, linearly polarized probe beam at 486 nm. As a result the weak probe beam “leaks” past an analyzer in the detection
channel and is measured using a PMT. This signal can be related to H atom density in the probe volume. A dye laser was
pumped by third harmonic of a Nd:YAG laser to create a laser beam at 486 nm. The 486-nm beam was frequency doubled to
a 243-nm beam. Use of the second scheme simplifies the TPP-PSP technique making it more convenient for diagnostics in
practical systems.
180
RE03
9:04 – 9:19
DEVELOPMENT OF COMBINED DUAL-PUMP VIBRATIONAL AND PURE-ROTATIONAL COHERENT ANTISTOKES RAMAN SCATTERING TECHNIQUE.
AMAN SATIJA, ROBERT P. LUCHT, Mechanical Engineering, Purdue University, West Lafayette, IN, USA.
in
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Coherent anti-Stokes Raman scattering is a parametric, four-wave mixing process. CARS, as a diagnostic technique, has
been used extensively for obtaining accurate temperature and species concentration information in non-reacting and reacting flows. Dual-pump vibrational CARS (DPVCARS) can provide quantitative temperature and concentration information
on multiple species in the probe volume. Mole-fraction information on molecules such as N2 , O2 , H2 and CO2 have been
obtained in flames with peak temperature in excess of 2000 K. Although DPVCARS provides high accuracy at higher temperatures it has low sensitivity at lower temperatures (below 800 K). Typically, pure-rotational CARS (PRCARS) provides
excellent sensitivity and precision at lower temperatures. We have combined DPVCARS and two-beam PRCARS into a
single system which employs three laser beams at different wavelengths. The accuracy and precision of the new combined
CARS system has been characterized in laminar flames. The system’s single-shot precision is better than 5.5 % between
295-2200 K, indicating its suitability for diagnostics in turbulent flames. The new system has been applied towards understanding flame structure of CH4 /H2 /air laminar flames, stabilized in a counter-flow burner. Here, we present results detailing
the development and application of the new combined CARS technique.
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RE04
9:21 – 9:36
VELOCITY MAP IMAGING STUDY OF THE PHOTOINITIATED CHARGE-TRANSFER DISSOCIATION OF
Cu+ (C6 H6 ) AND Ag+ (C6 H6 )
JON MANER, DANIEL MAUNEY, MICHAEL A DUNCAN, Department of Chemistry, University of Georgia,
Athens, GA, USA.
M+ (C6 H6 ) (M = Cu, Ag) complexes are generated in the gas phase by laser vaporization and detected in a reflectron timeof-flight mass spectrometer. Excitation of M+ (C6 H6 ) at 355 nm results exclusively in dissociative charge transfer, leading to
neutral M and C6 H6 + products for both Cu and Ag complexes. Kinetic energy release in translationally hot C6 H6 + fragments
is detected using a new apparatus designed for photofragment imaging of mass-selected ion beams. Velocity map imaging and
slice imaging techniques are employed. Analysis of the data provide new information on the binding energies of Cu+ (C6 H6 )
and Ag+ (C6 H6 ).
Intermission
RE05
9:55 – 10:10
MID-IR CAVITY RINGDOWN SPECTROSCOPY FOR ATMOSPHERIC ETHANE ABUNDANCE MEASUREMENTS
LINHAN SHEN, THINH QUOC BUI, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA; LANCE CHRISTENSEN, Science Division, Jet Propulsion Laboratory/Caltech, Pasadena, CA, USA; MITCHIO OKUMURA, Division of Chemistry and Chemical Engineering,
California Institute of Technology, Pasadena, CA, USA.
We demonstrate a mid-IR (3.3 µm) cw cavity ringdown spectrometer capable of measuring atmospheric ethane abundances. This technique can measure atmospheric ethane concentration as low as 100 ppb. The atmospheric ethane to methane
ratio could also be observed by measuring methane concentration using a high precision near-IR (1.65 µm) cavity ringdown
spectrometer. We will also discuss the daily variation of ethane abundance and ethane to methane ratio in Pasadena observed
using this tecnhique.
181
RE06
STRONG THERMAL NONEQUILIBRIUM IN HYPERSONIC CO AND CH4 PROBED BY CRDS
10:12 – 10:27
ar
y
MAUD LOUVIOT, Laboratoire ICB, CNRS/Université de Bourgogne, DIJON, France; NICOLAS SUASDAVID, IPR UMR6251, CNRS - Université Rennes 1, Rennes, France; VINCENT BOUDON, Laboratoire
ICB, CNRS/Université de Bourgogne, DIJON, France; ROBERT GEORGES, IPR UMR6251, CNRS - Université Rennes 1, Rennes, France; MICHAEL REY, Groupe de Spectrométrie Moléculaire et Atmosphérique,
UMR CNRS 7331, Université de Reims, Reims Cedex 2, France; SAMIR KASSI, UMR5588 LIPhy, Université
Grenoble 1/CNRS, Saint Martin D’heres, France.
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A new experimental set-up coupling a High Enthalpy Source (HES) reaching 2000 K to a cw Cavity Ring-Down Spectrometer has been developed to investigate rotationnally cold hot bands of polyatomic molecules in the [1.5, 1.7] µm region.
The rotational and vibrational molecular degrees of freedom are strongly decoupled in the hypersonic expansion produced
by the HES and probed by Cavity Ring-Down Spectroscopy. Carbon monoxide has been used as a first test molecule to
validate the experimental approach. Its expansion in argon led to rotational and vibrational temperatures of 6.7 ± 0.8 K and
2006 ± 476 K, respectively. The Tetradecad polyad of methane (1.67 µm) was investigated under similar conditions leading
to rotational and vibrational temperatures of 13 ± 5 K and 750 ± 100 K, respectively. The rotationally cold structure of the
spectra reveals many hot bands involving highly excited vibrational states of methane.
RE07
ROTATIONALLY-RESOLVED INFRARED SPECTROSCOPY OF THE ν16 BAND OF 1,3,5-TRIOXANE
10:29 – 10:44
BRADLEY M. GIBSON, NICOLE KOEPPEN, Department of Chemistry, University of Illinois at UrbanaChampaign, Urbana, IL, USA; BENJAMIN J. McCALL, Departments of Chemistry and Astronomy, University
of Illinois at Urbana-Champaign, Urbana, IL, USA.
1,3,5-trioxane is the simplest cyclic form of polyoxymethylene (POM), a class of formaldehyde polymers that has been
proposed as the origin of distributed formaldehyde formation in comet comae and a potential source of formaldehyde in
prebiotic chemistry. Although claimed POM detections have since been proven to be inconclusive, laboratory simulations of
cometary conditions have yielded trioxane and other POMsa .
While the microwave spectrum of 1,3,5-trioxane has been studied extensivelyb , to date only one rotationally-resolved rovibrational spectrum has been publishedc . Here, we present our studies of the ν16 band of gas-phase trioxane centered at 1177
cm−1 . Trioxane was entrained in a supersonic expansion of argon and characterized by continuous-wave cavity ringdown
spectroscopy using an etalon-stabilized external-cavity quantum cascade laserd . Rotationally resolved spectra were obtained
with less than 15 MHz resolution.
a
Cottin, H., Bénilan, Y., Gazeau, M-C., and Raulin, F. Origin of Cometary Extended Sources from Degradation of Refractory Organics on Grains: Polyoxymethylene as
Formaldehyde Parent Molecule. Icarus 167 (2004), 397-416.
b
Oka, T., Tsuchiya, K., Iwata, S., and Morino, Y. Microwave Spectrum of s-Trioxane. Bull. Chem. Soc. Jpn. 37 (1964), 4-7.
c
Henninot, J-F., Bolvin, H., Demaison, J., and Lemoine, B. The Infrared Spectrum of Trioxane in a Supersonic Slit Jet. J. Mol. Spect. 152 (1992), 62-68.
d
Gibson, B.M. and McCall, B.J., contribution TJ08, presented at the 69th International Symposium on Molecular Spectroscopy, Urbana, IL, USA, 2014.
182
RE08
10:46 – 11:01
IMPROVING SNR IN TIME-RESOLVED SPECTROSCOPIES WITHOUT SACRIFICING TEMPORAL-RESOLUTION:
APPLICATION TO THE UV PHOTOLYSIS OF METHYL CYANOFORMATE
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MICHAEL J. WILHELM, JONATHAN M. SMITH, HAI-LUNG DAI, Department of Chemistry, Temple University, Philadelphia, PA, USA.
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We demonstrate a new analysis for the enhancement of
the signal-to-noise ratio (SNR) in time-resolved spectroscopies,
termed spectral reconstruction analysis (SRA). As distinct from
a simple linear average which produces only a single representative spectrum with enhanced SNR, SRA produces a comparable
enhancement, but fully preserves the measured time-dependence.
Specifically, given a series of (n) time-resolved spectra, SRA
yields an approximate sqrt(n) SNR enhancement for each of the
original n-spectra. SRA operates by eliminating noise in the temporal domain, thereby significantly attenuating noise in the spectral domain, as follows (see Figure): Temporal profiles of each
measured frequency are fit to capture the representative temporal
evolutions, then time-resolved spectra are reconstructed by replacing the measured profiles with the fit profiles.
In addition to simulated control data sets, we demonstrate
SRA with experimentally measured time-resolved IR emission spectra, collected following the 193 nm photolysis of methyl
cyanoformate (CH3 OC(O)CN). Of significance, we now show the appearance of resonances assignable to hydrogen cyanide
(HCN), which were previously obscured in the noise of the measured spectra. The presence of HCN suggests the occurrence
of a previously uncharacterized dissociation channel, likely involving a cyclic 5-center transition state.
RE09
11:03 – 11:18
LASER-INDUCED PLASMAS IN AMBIENT AIR FOR INCOHERENT BROADBAND CAVITY-ENHANCED ABSORPTION SPECTROSCOPY
ALBERT A RUTH, SOPHIE DIXNEUF, Physics Department and Environmental Research Institute, University
College Cork, Cork, Ireland; JOHANNES ORPHAL, Institute for Meteorology and Climate Research, Karlsruhe
Institute of Technology, 76344 Eggenstein-Leopoldshafen, Germany.
The emission from a laser-induced plasma in ambient air, generated by a high power femtosecond laser, was utilized as
pulsed incoherent broadband light source in the center of a quasi-confocal high finesse cavity. The time dependent spectra
of the light leaking from the cavity was compared with those of the laser-induced plasma emission without the cavity. It was
found that the light emission was sustained by the cavity despite the initially large optical losses of the laser-induced plasma
in the cavity. The light sustained by the cavity was used to measure part of the S1 ← S0 absorption spectrum of gaseous
azulene at its vapour pressure at room temperature in ambient air as well as the strongly forbidden γ–band in molecular
′
3 − ′′
oxygen: b1 Σ+
g (ν = 2) ← X Σg (ν = 0)
183
RF. Atmospheric science
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Chair: Joseph Hodges, National Institute of Standards and Technology, Gaithersburg, MD, USA
RF01
PHOTOACOUSTIC SPECTROSCOPY OF THE OXYGEN A-BAND
1:30 – 1:40
ELIZABETH M LUNNY, THINH QUOC BUI, Division of Chemistry and Chemical Engineering, California
Institute of Technology, Pasadena, CA, USA; CAITLIN BRAY, Department of Chemistry, Wesleyan University,
Middletown, CT, USA; PRIYANKA RUPASINGHE, Physical Sciences, Cameron University, Lawton, OK, USA;
MITCHIO OKUMURA, Division of Chemistry and Chemical Engineering, California Institute of Technology,
Pasadena, CA, USA.
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The oxygen A-band (760 nm) is used in a number of remote sensing applications due to the precisely known, uniform
distribution of molecular oxygen throughout the atmosphere and the spectral isolation of the band. The A-band is used to
determine the pathlength of solar radiation for OCO-2, a current NASA mission which seeks to measure the global sources
and sinks of carbon dioxide at unprecedented spatial and temporal resolution. The goal of measuring atmospheric carbon
dioxide concentrations with a precision of 0.25% requires a precise knowledge of line shape parameters. Currently, the most
significant uncertainties in A-band spectroscopy result from line mixing and collision induced absorption, which become
more prominent at elevated pressures. Photoacoustic spectroscopy is ideal to observe these phenomena due to the large
dynamic range and zero-background advantages of the technique. Photoacoustic spectra of the oxygen A-band over a range
of pressures will be presented in addition to line shape parameters extracted from multispectrum fits of the data.
RF02
HIGH PRESSURE OXYGEN A-BAND SPECTRA
1:42 – 1:57
BRIAN DROUIN, KEEYOON SUNG, SHANSHAN YU, Jet Propulsion Laboratory, California Institute of
Technology, Pasadena, CA, USA; ELIZABETH M LUNNY, THINH QUOC BUI, MITCHIO OKUMURA,
Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA;
PRIYANKA RUPASINGHE, Physical Sciences, Cameron University, Lawton, OK, USA; CAITLIN BRAY, Department of Chemistry, Wesleyan University, Middletown, CT, USA; DAVID A. LONG, JOSEPH HODGES,
Chemical Sciences Division, National Institute of Standards and Technology, Gaithersburg, MD, USA; DAVID
ROBICHAUD, Biomass Molecular Science , National Renewable Energy Laboratory , Golden, CO, USA; D.
CHRIS BENNER, V. MALATHY DEVI, JIAJUN HOO, Department of Physics, College of William and Mary,
Williamsburg, VA, USA.
Composition measurements from remote sensing platforms require knowledge of air mass to better than the desired
precision of the composition. Oxygen spectra allow determination of air mass since the mixing ratio of oxygen is fixed. The
OCO-2 mission is currently retrieving carbon dioxide concentration using the oxygen A-band for air mass normalization.
The 0.25% accuracy desired for the carbon dioxide concentration has pushed the state-of-the-art for oxygen spectroscopy. To
produce atmospheric pressure A-band cross-sections with this accuracy requires a sophisticated line-shape model (Galatry or
Speed-Dependent) with line mixing (LM) and collision induced absorption (CIA). Models of each of these phenomena exist,
but an integrated self-consistent model must be developed to ensure accuracy.
This presentation will describe the ongoing effort to parameterize these phenomena on a representative data set created
from complementary experimental techniques. The techniques include Fourier transform spectroscopy (FTS), photo-acoustic
spectroscopy (PAS) and cavity ring-down spectroscopy (CRDS). CRDS data allow long-pathlength measurements with absolute intensities, providing lineshape information as well as LM and CIA, however the subtleties of the lineshape are diminished
in the saturated line-centers. Conversely, the short paths and large dynamic range of the PAS data allow the full lineshape to
be discerned, but with an arbitrary intensity axis. Finally, the FTS data provides intermediate paths and consistency across a
broad pressure range. These spectra are all modeled with the Labfit software using first the spectral line database HITRAN,
and then model values are adjusted and fitted for better agreement with the data.
184
RF03
1:59 – 2:14
1
COLLISION-DEPENDENT LINE AREAS IN THE a ∆g ← X
3
Σ−
g
BAND OF MOLECULAR OXYGEN
VINCENT SIRONNEAU, ADAM J. FLEISHER, JOSEPH HODGES, Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, MD, USA.
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We report precise line areas for individual rotationally resolved transitions within the a1 ∆g ← X 3 Σ−
g electronic band
of molecular oxygen recorded as a function of pressure for both neat samples of O2 as well as samples of O2 dilute with a
variety of collisional partners. Using optical frequency comb referenced frequency-stabilized cavity ring-down spectroscopy
(FS-CRDS) near 1.27 µm we measure line areas with a quality-of-fit QF ≤ 50,000 using a partially correlated quadraticspeed-dependent Nelkin-Ghatak profile. This spectrometer has achieved this high QF by both suppressing coupled cavity
effects and by preserving a high-fidelity frequency axis with absolute frequency accuracy approaching 1 part in 109 . With
this instrument we are also currently exploring collision-induced absorption (CIA) and perturbative line mixing effects in O2
over the entire 7800-7940 cm−1 spectral range.
RF04
ANOMALOUS CENTRIFUGAL DISTORTION IN HDO AND SPECTROSCOPIC DATA BASES
2:16 – 2:31
L. H. COUDERT, CNRS et Universités Paris Est et Paris Diderot, LISA, Creteil, France.
The HDO molecule is important from the atmospheric point of view as it can be used to study the water cycle in the earth
atmosphere.a It is also interesting from the spectroscopic point of view as it displays an anomalous centrifugal distortion
similar to that of the normal species H2 O. A model developed to treat the anomalous distortion in HDO should account for
the fact that it lacks a two-fold axis of symmetry.
A new treatment aimed at the calculation of the rovibrational energy of the HDO molecule and allowing for anomalous
centrifugal distortion effects has been developed. It is based on an effective Hamiltonian in which the large amplitude bending
ν2 mode and the overall rotation of the molecule are treated simultaneously.b Due to the lack of a two-fold axis of symmetry,
this effective Hamiltonian contains terms arising from the non-diagonal component of the inertia tensor and from the Corioliscoupling between the large amplitude bending ν2 mode and the overall rotation of the molecule.
This new treatment has been used to perform a line position analysis of a large body of infrared,c microwave,d and hot
water vapore data involving the ground and (010) states up to J = 22. For these 4413 data, a unitless standard deviation of
1.1 was achieved. A line intensity analysis was also carried out and allowed us to reproduce the strength of 1316 transitionsc
with a unitless standard deviation of 1.1.
In the talk, the new theoretical approach will be presented. The results of both analyses will be discussed and compared
with those of a previous investigation.f The new spectroscopic data base built will be compared with HITRAN 2012.g
a
Herbin et al., Atmos. Chem. Phys. 9 (2009) 9433; and Schneider and Hase, Atmos. Chem. Phys. 11 (2011) 11207.
Coudert, Wagner, Birk, Baranov, Lafferty, and Flaud, J. Molec. Spectrosc. 251 (2008) 339.
c
Johns, J. Opt. Soc. Am. B 2 (1985) 1340; Toth, J. Molec. Spectrosc. 162 (1993) 20; Paso and Horneman, J. Opt. Soc. Am. B 12 (1995) 1813; and Toth, J. Molec. Spectrosc. 195
(1999) 73.
d
Messer, De Lucia, and Helminger, J. Molec. Spectrosc. 105 (1984) 139; and Baskakov et al., Opt. Spectrosc. 63 (1987) 1016.
e
Parekunnel et al., J. Molec. Spectrosc. 210 (2001) 28; and Janca et al., J. Molec. Specrosc. 219 (2003) 132.
f
Tennyson et al., J. Quant. Spectrosc. Radiat. Transfer 111 (2010) 2160.
g
Rothman et al., J. Quant. Spectrosc. Radiat. Transfer 130 (2013) 4.
b
185
RF05
2:33 – 2:48
SPEED-DEPENDENT BROADENING AND LINE-MIXING IN CH4 PERTURBED BY AIR NEAR 1.64 µm FOR THE
FRENCH/GERMAN CLIMATE MISSION MERLIN
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THIBAULT DELAHAYE, THI NGOC HA TRAN, CNRS et Universités Paris Est et Paris Diderot, Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA), Créteil, France; ZACHARY REED, STEPHEN E
MAXWELL, JOSEPH HODGES, Chemical Sciences Division, National Institute of Standards and Technology,
Gaithersburg, MD, USA.
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Climate change is one of the greatest challenges presently facing mankind, and methane is one of the most powerful
anthropogenic greenhouse gases. For a better understanding of future climate trends, a satellite dedicated to the measurements
of atmospheric methane is under joint development by the French and German space research centers (CNES and DLR).
The so-called MERLIN mission (Methane Remote Sensing Lidar Mission, 2019) aims at providing global information on
atmospheric methane concentration with a relative uncertainty less than 2% and with a spatial resolution of 50 kma . Such
spectroscopic monitoring of gases in the atmosphere of the Earth, requires a precise description of absorption lines shapes
that goes beyond the usual Voigt profile (VP). In the case of methane, the differences between the measured profiles and those
given by the VP can be very important b , making the VP completely incompatible with the reliable detection of sources and
sinks from space. In this work, we present the first results on the modeling of methane lines broadened by air in the 1.64
µm region and the associated spectroscopic parameters, taking into account various collisional effects between molecules
that are neglected by the VP: collisional interference between the lines (line-mixing), collision-induced velocity changes
(Dicke narrowing effect) and speed dependence of the collisional broadening and shifting. These results were obtained by
simultaneously fitting the model parameters to high sensitivity and high-resolution cavity ring-down spectroscopy (CRDS)
spectra recorded at the National Institute of Standards and Technology (NIST) over a wide pressure range (5 to 100 kPa).
These spectroscopic data and the associated model to calculate the spectrum absorption coefficient will be then used to
analyze ground-based atmospheric spectra at the TCCON facility in Park Falls, Wisconsin.
a
b
C. Kiemle, M. Quatrevalet, G. Ehret et al., Atmos. Meas. Tech. 4 (2011)
H. Tran, J.-M. Hartmann, G. Toon et al., Journal of Quant. Spectrosc. Radia. Trans. 111 (2010)
RF06
2:50 – 3:05
MID INFRARED DUAL FREQUENCY COMB SPECTROMETER FOR THE DETECTION OF METHANE IN AMBIENT AIR
HANS SCHUESSLER, FENG ZHU, Department of Physics and Astronomy, Texas A&M University, College
Station, TX, USA; ALEXANDER KOLOMENSKII, Department of Physics and Astronomy, Texas A & M University, college station, TX, USA.
We demonstrate using mid infrared dual frequency comb spectroscopy for the detection of methane in ambient air. The
mid infrared frequency comb sources based on femtosecond Er fiber oscillators are produced through difference frequency
generation with periodically poled MgO doped lithium niobate crystals and stabilized at slightly different repetition rates
at about 250 MHz. We performed dual frequency comb spectroscopy in the spectral range between 2900 cm−1 and 3150
cm−1 with 0.07 cm−1 resolution using a multipass cell of about 580 meter path length, and achieved the sensitivity about
7.6E-7 cm−1 with 80 ms data acquisition time. We determined the methane concentration as about 1.5 ppmv in the ambient
air of the laboratory, and the minimum detection limit as about 60 ppbv for the current setup.
This work was funded by the Robert A. Welch Foundation, Grant No. A1546 and the Qatar Foundation under Grant No.
NPRP 6-465-1-091.
186
RF07
3:07 – 3:22
IMPROVED OZONE AND CARBON MONOXIDE PROFILE RETRIEVALS USING MULTISPECTRAL MEASUREMENTS FROM NASA “A TRAIN”, NPP, AND TROPOMI SATELLITES
DEJIAN FU, Jet Propulsion Laboratory, California Institute of Technology , PASADENA, CAL, USA.
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Tropospheric ozone is at the juncture of air quality and climate. Ozone directly impacts human health, is a phytotoxin
that undermines carbon uptake, and directly forces the climate system through absorption of thermal radiation. Carbon
monoxide is a chemical precursor of greenhouse gases CO2 and tropospheric O3 , and is also an ideal tracer of transport
processes due to its medium life times (weeks to months). The Aqua-AIRS and Aura-OMI instruments in the NASA “ATrain”, CrIS and OMPS instruments on the NOAA Suomi-NPP, IASI and GOME-2 on METOP, TROPOMI aboard the
Sentinel 5 precursor (S5p) have the potential to provide the synoptic chemical and dynamical context for ozone necessary to
quantify long-range transport at global scales and as an anchor to the near-term constellation of geostationary sounders: NASA
TEMPO, ESA Sentinel 4, and the Korean GEMS. We introduce the JPL Multi-Spectral, Multi-Species, Multi-Satellite (MS)3
retrieval algorithm, which ingests panspectral observations across multiple platforms in an non-linear optimal estimation
framework. It incorporates the advances in remote sensing science developed during EOS-Aura era including rigorous error
analysis diagnostics and observation operators needed for trend analysis, climate model evaluation, and data assimilation.
Its performances have been demonstrated through prototype studies for multi-satellite missions (AIRS, CrIS, TROPOMI,
TES, OMI, and OMPS). We present the preliminary joint tropospheric ozone retrievals from AIRS/OMI and CrIS/OMPS,
and demonstrate the potential of joint carbon monoxide profiles from TROPOMI/CrIS. These results indicate that ozone can
be retrieved with 2 degrees of freedom for signal (dofs). The joint ozone retrievals are closer to ozone retrieved from the
NASA Tropospheric Emission Spectrometer than any single instruments retrievals. Joint CO profiles have a dofs similar to
the MOPITT multispectral retrieval. Consequently, multispectral retrievals show promise in providing continuity with NASA
EOS observations and paving the way towards a new advanced atmospheric composition constellation. To further improve
the quality of measurements using multiple spectral regions, next generation of ozone and carbon monoxide spectroscopic
parameters should mitigate the existing discrepancies among different spectral regions (microwave, thermal infrared, visible
and ultraviolet).
RF08
3:24 – 3:39
TEMPERATURE DEPENDENCES OF AIR-BROADENING AND SHIFT PARAMETERS IN THE ν3 BAND OF OZONE
MARY ANN H. SMITH, Science Directorate, NASA Langley Research Center, Hampton, VA, USA; V.
MALATHY DEVI, D. CHRIS BENNER, Department of Physics, College of William and Mary, Williamsburg,
VA, USA.
Line parameter errors can contribute significantly to the total errors in retrievals of terrestrial atmospheric ozone concentration profiles using the strong 9.6-µm band, particularly for nadir-viewing experimentsa . Detailed knowledge of the
interfering ozone signal is also needed for retrievals of other atmospheric speciesb in this spectral region. We have determined
Lorentz air-broadening and pressure-induced shift coefficients along with their temperature dependences for a number of
transitions in the ν3 fundamental band of 16 O3 . These results were obtained by applying the multispectrum nonlinear leastsquares fitting techniquec to a set of 31 high-resolution infrared absorption spectra of O3 recorded at temperatures between
160 and 300 K with several different room-temperature and coolable sample cells at the McMath-Pierce Fourier transform
spectrometer at the National Solar Observatory on Kitt Peak. We compare our results with other available measurements and
with the ozone line parameters in the HITRAN databased .
a
J. Worden et al., J. Geophys. Res. 109 (2004) 9308-9319.
R. Beer et al., Geophys. Res. Lett. 35 (2008) L09801.
c
D. Chris Benner et al., JQSRT 53 (1995) 705-721.
d
L. S. Rothman et al., JQSRT 130 (2013) 4-50.
b
Intermission
187
RF09
3:58 – 4:13
3
MICROWAVE OPTICAL DOUBLE RESONANCE STUDIES OF PERTURBATIONS IN THE SO A Π STATE
ar
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ANDREW RICHARD WHITEHILL, Earth, Atmospheric, and Planetary Sciences, MIT, Cambridge, MA, USA;
ALEXANDER W. HULL, TREVOR J. ERICKSON, JUN JIANG, CARRIE WOMACK, BARRATT PARK, Department of Chemistry, MIT, Cambridge, MA, USA; SHUHEI ONO, Earth, Atmospheric, and Planetary Sciences,
MIT, Cambridge, MA, USA; ROBERT W FIELD, Department of Chemistry, MIT, Cambridge, MA, USA.
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There is a possibility that perturbations of the SO A3 Π state provide a mechanism for photodissociation of SO by a
1 + 1′ two-color solar radiation process. The resultant S atom photofragments could depart from the isotopologue natural
abundance ratios. The SO A3 Π–X3 Σ− transition is very weak and the radiative lifetimes of v < 4 levels of the A3 Π state
are > 10 µs. The lowest vibrational levels of the A3 Π state are perturbed by high vibrational levels of three metastable
states: c 1 Σ− , A′ 3 ∆, and A′′ 3 Σ+ . If some upper atmospheric photophysical process were to populate the SO c, A′ , and A′′
states, emission from these states would escape detection. A↔(c, A′ , A′′ ) perturbations by the various S isotopologues will
culminate at widely separated values of J, with the result that, for some isotopologues, the perturbations are located outside
of the region of thermally populated rotational levels. These perturbations are exceptionally difficult to characterize by Laser
Induced Fluorescence. In addition to Chirped Pulse millimeter-Wave (CPmmW) spectroscopy in the A3 Π state, we are using
Coherence Converted Population Transfer (CCPT) in the X3 Σ− state, an especially sensitive form of microwave-detected
Microwave Optical Double Resonance, in order to characterize the A3 Π state and its perturbers.
RF10
4:15 – 4:30
VALIDATION OF A NEW HNO3 LINE PARAMETERS AT 7.6 µm USING LABORATORY INTENSITY MEASUREMENTS AND MIPAS SATELLITE SPECTRA
MARCO RIDOLFI, Dipartimento di Fisica e Astronomia , Università di Bologna, Bologna, Italy;
AGNES PERRIN, JEAN-MARIE FLAUD, LISA, CNRS, Universités Paris Est Créteil et Paris Diderot, Créteil,
France; JEAN VANDER AUWERA, Service de Chimie Quantique et Photophysique, Université Libre de Bruxelles, Brussels, Belgium; MASSIMO CARLOTTI, Dipartimento di Chimica Industriale ”Toso Montanari”, Università di Bologna, Bologna, Italy.
A new set of line parameters (positions, intensities and line widths) for nitric acid has been generated in the 7.6 µm region
using the results of recent high quality experimental laboratory studies and of theoretical calculations. The validation of this
new database was performed thanks to limb emission radiances measured in 2002-2012 by the ”Michelson Interferometer
for Passive Atmospheric Sounding” (MIPAS) instrument on board the ENVISAT satellite. This study will help to improve
HNO3 satellite retrievals by allowing measurements to be performed using simultaneously 11 µm and 7.6 µm microwindows.
Hopefully this will be the case for the forthcoming Infrared Atmospheric Sounding Interferometer New Generation (IASING) instrument developed by CNES. IASI-NG will be the key payload element of the future METOP Second Generation
(METOP-SG) series of EUMETSAT meteorological polar-orbit satellites.
188
RF11
4:32 – 4:47
ROTATIONAL SPECTROSCOPY OF NEWLY DETECTED ATMOSPHERIC OZONE DEPLETERS: CF3 CH2 Cl,
CF3 CCl3 , AND CF2 ClCCl3
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ZBIGNIEW KISIEL, EWA BIAŁKOWSKA-JAWORSKA, LECH PSZCZÓŁKOWSKI, ON2, Institute of
Physics, Polish Academy of Sciences, Warszawa, Poland; ICIAR URIARTE, PATRICIA ECIJA, FRANCISCO
J. BASTERRETXEA, EMILIO J. COCINERO, Departamento de Quı́mica Fı́sica, Universidad del Paı́s Vasco
(UPV-EHU), Bilbao, Spain.
In a recent study of unpolluted air samples from Tasmania and of deep firn snow in Greenland four previously overlooked
ozone-depleting substances have been identified.a These compounds started to emerge in the atmosphere in the 1960s, and
two: CF3 CCl3 (CFC-113a) and CF3 CH2 Cl (HCHF-133a) continue to accumulate in the atmosphere.
a
in
Three of the four compounds have non-zero dipole moments and are amenable to study by rotational spectroscopy,
establishing the basis for analytic applications. Relatively limited studies have been reported for CF3 CH2 Clb and CF3 CCl3 ,c,d
while CF2 ClCCl3 has not yet been studied by this technique. We presently report extensive results obtained for all three
compounds, resulting from concerted application of supersonic expansion FTMW spectroscopy in chirped pulse and cavity
modes, and room-temperature MMW spectroscopy. Among the plentiful results, we have been able to resolve and fit the
complex nuclear quadrupole hyperfine splitting.
J.C.Laube, et al., Nature Geoscience 7, 266 (2014).
T.Ogata, et al., J. Mol. Struct. 144, 1 (1986).
c
R.Holm, et al., Z. Naturforsch. 23a, 1040 (1968).
d
J.H.Carpenter et al., J. Mol. Spectrosc. 154, 207 (1992); P.J.Seo et al., J. Mol. Spectrosc. 169, 58 (1995).
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RF12
4:49 – 5:04
CHIRPED PULSE AND CAVITY FT MICROWAVE SPECTROSCOPY OF THE FORMIC ACID – TRIMETHYLAMINE
WEAKLY BOUND COMPLEX
BECCA MACKENZIE, CHRIS DEWBERRY, KEN LEOPOLD, Chemistry Department, University of Minnesota, Minneapolis, MN, USA.
Amine-carboxylic acid interactions are important in many biological systems and have recently received attention for
their role in the formation of atmospheric aerosols. Here, we study the molecular and electronic structure of the formic
acid – trimethylamine complex, using it as a model for amine-carboxylic acid interactions. The microwave spectrum of the
complex has been observed using chirped pulse and conventional cavity-type Fourier transform microwave spectroscopy. The
degree of proton transfer has been assessed using the 14 N nuclear quadrupole hyperfine structure. Experimental results will
be compared to DFT calculations.
RF13
5:06 – 5:21
FORMIC SULFURIC ANHYDRIDE: A NEW CHEMICAL SPECIES WITH POSSIBLE IMPLICATIONS FOR ATMOSPHERIC AEROSOL
BECCA MACKENZIE, CHRIS DEWBERRY, KEN LEOPOLD, Chemistry Department, University of Minnesota, Minneapolis, MN, USA.
Aerosols are important players in the Earth’s atmosphere, affecting climate, cloud formation, and human health. In this
work, we report the discovery of a previously unknown molecule, formic sulfuric anhydride (FSA), that may influence the
formation and composition of atmospheric aerosol particles. Five isotopologues of FSA have been observed by microwave
spectroscopy and further characterized using DFT calculations. The system has dipole moment components along all three
inertial axes, and indeed a, b, and c-type transitions have been observed. A π 2 + π 2 + σ 2 cycloaddition reaction between SO3
and HCOOH is proposed as a possible mechanism for the formation of FSA and calculations indicate that the transformation
is effectively barrierless. Facile formation of the anhydride followed by hydrolysis in small water-containing clusters or liquid
droplets may provide a mechanism of incorporating volatile organics into atmospheric aerosol. We suggest that FSA and its
derivatives be considered in future atmospheric and climate models.
189
RF14
ROTATIONAL SPECTROSCOPY OF METHYL VINYL KETONE
5:23 – 5:38
OLENA ZAKHARENKO, R. A. MOTIYENKO, JUAN-RAMON AVILES MORENO, T. R. HUET, Laboratoire
PhLAM, UMR8523 CNRS - Université Lille 1, Villeneuve d’Ascq, France.
in
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Methyl vinyl ketone, MVK, along with previously studied by our team methacrolein, is a major oxidation product of
isoprene, which is one of the primary contributors to annual global VOC emissions. In this talk we present the analysis of
the rotational spectrum of MVK recorded at room temperature in the 50 – 650 GHz region using the Lille spectrometer. The
spectroscopic characterization of MVK ground state will be useful in the detailed analysis of high resolution infrared spectra.
Our study is supported by high level quantum chemical calculations to model the structure of the two stable s-trans and s-cis
conformers and to obtain the harmonic force field parameters, internal rotation barrier heights, and vibrational frequencies.
In the Doppler-limited spectra the splittings due to the internal rotation of methyl group are resolved, therefore for analysis
of this molecule we used the Rho-Axis-Method Hamiltonian and RAM36 code to fit the rotational transitions. At the present
time the ground state of two conformers is analyzed. Also we intend to study some low lying excited states. The analysis is
in progress and the latest results will be presented.
Support from the French Laboratoire d’Excellence CaPPA (Chemical and Physical Properties of the Atmosphere) through
contract ANR-10-LABX-0005 of the Programme d’Investissements d’Avenir is acknowledged.
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RF15
5:40 – 5:55
THE MILLIMETER-WAVE SPECTRUM OF METHACROLEIN. TORSION-ROTATION-VIBRATION EFFECTS IN THE
EXCITED STATES
OLENA ZAKHARENKO, R. A. MOTIYENKO, JUAN-RAMON AVILES MORENO, T. R. HUET, Laboratoire
PhLAM, UMR8523 CNRS - Université Lille 1, Villeneuve d’Ascq, France.
Last year we reported the analysis of the rotational spectrum of s-trans conformer of methacrolein CH2 =C(CH3 )CHO in
the ground vibrational statea . In this talk we report the study of its low lying excited vibrational states. The study is based on
room-temperature absorption spectra of methacrolein recorded in the frequency range 150 – 465 GHz using the spectrometer
in Lille. The new results include assignment of the first excited torsional state (131 cm−1 ), and the joint analysis of the
vt = 0 and vt = 1 states, that allowed us to improve the model in the frame of Rho-Axis-Method (RAM) Hamiltonian and
to remove some strong correlations between parameters. Also we assigned the first excited vibrational state of the skeletal
torsion mode (170 cm−1 ). The inverse sequence of A and E tunneling substates as well as anomalous A-E splittings observed
for the rotational lines of vsk = 1 state clearly indicate a coupling between methyl torsion and skeletal torsion. However we
were able to fit within experimental accuracy the rotational lines of vsk = 1 state using the RAM Hamiltonian. Because of
the inversion of the A and E tunneling substates the rotational lines of the vsk = 1 states were assumed to belong to a virtual
first excited torsional state. Finally, we assigned several low-Ka rotational transitions of the excited vibrational states above
200 cm−1 but their analysis is complicated by different rotation-vibration interactions. In particular there is an evidence of
the Fermi-type resonance between the second excited torsional state and the first excited state of the in-plane skeletal bending
mode (265 cm−1 ).
Support from the French Laboratoire d’Excellence CaPPA (Chemical and Physical Properties of the Atmosphere) through
contract ANR-10-LABX-0005 of the Programme d’Investissements d’Avenir is acknowledged.
a
Zakharenko O. et al., 69th ISMS, 2014, TI01
190
RG. Vibrational structure/frequencies
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Chair: John F. Stanton, The University of Texas, Austin, TX, USA
RG01
ALKYL CH STRETCH VIBRATIONS AS A PROBE OF LOCAL ENVIRONMENT AND STRUCTURE
1:30 – 1:45
in
EDWIN SIBERT, DANIEL P. TABOR, Department of Chemistry, The Univeristy of Wisconsin, Madison, WI,
USA; NATHANAEL KIDWELL, JACOB C. DEAN, TIMOTHY S. ZWIER, Department of Chemistry, Purdue
University, West Lafayette, IN, USA.
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The CH stretch region is a good candidate as a probe of structure and local environment. The functional groups are
ubiquitous and their vibration spectra exhibit a surprising sensitivity to molecular structure. In this talk we briefly review
our theoretical model Hamiltonian [J. Chem. Phys. 138 064308 (2013)] for describing vibrational spectra associated with
the CH stretch of CH2 groups and then describe an extension of it to molecules containing methyl and methoxy groups.
Results are compared to the infrared spectroscopy of four molecules studied under supersonic expansion cooling in gas
phase conditions. The molecules include 1,1-diphenylethane, 1,1-diphenylpropane, 2-methoxyphenol (guaiacol), and 1,3dimethoxy-2-hydroxybenzene (syringol). The curvilinear local-mode Hamiltonian predicts most of the major spectral features
considered in this study and provides insights into mode mixing. We conclude by returning to CH2 groups and explain both
why the CH stretch spectrum of cyclohexane is substantially modified when it forms a complex with an alkali metal and what
these spectra tell us about the structure of the complex.
RG02
1:47 – 2:02
COMPUTING THE VIBRATIONAL ENERGIES OF CH2 O AND CH3 CN WITH PHASE-SPACED LOCALIZED FUNCTIONS AND AN ITERATIVE EIGENSOLVER
JAMES BROWN, TUCKER CARRINGTON, Department of Chemistry, Queen’s University, Kingston, ON,
Canada.
For decades scientists have attempted to use ideas of classical mechanics to choose basis functions for calculating
spectra. The hope is that a classically-motivated basis set will be small because it covers only the dynamically important
part of phase space. One popular idea is to use phase-space localized (PSL) basis functions. Because the overlap matrix, in
the matrix eigenvalue problem obtained by using PSL functions with the variational method, is not an identity, it is costly to
use iterative methods to solve the matrix eigenvalue problem. Iterative methods are imperative if one wishes to avoid storing
matrices which is important for larger molecules. Recentlya we showed it was possible to circumvent the orthogonality
(overlap) problem and use iterative eigensolvers. Here, we present calculated vibrational energies of CH2 O and CH3 CN
using the iterative Arnoldi algorithm and PSL functions, and show that our PSL basis is competitive with other previously
used basis sets for these molecules.
a
J. Brown and T. Carrington Jr., Phys. Rev. Lett. 114, 058901 (2015).
191
RG03
2:04 – 2:19
A MULTILAYER SUM-OF-PRODUCTS METHOD FOR COMPUTING VIBRATIONAL SPECTRA WITHOUT STORING FULL-DIMENSIONAL VECTORS OR MATRCIES
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PHILLIP THOMAS, TUCKER CARRINGTON, Department of Chemistry, Queen’s University, Kingston, ON,
Canada.
in
By optimizing sum-of-products (SOP) basis functions, it is possible to compute vibrational spectra, using a direct product
basis, without storing vectors with as many components as there are product basis functions. These ideas are presented in a
recent paper: Leclerc and Carrington, J. Chem. Phys 140 174111 (2014). In that paper, the SOP basis functions are products
of factors that depend on a single coordinate. When using factors that depend on one coordinate the number of terms (rank)
in the SOP basis functions increases with the size of the molecule and the coupling strength. Using multi-dimensional factors
makes it possible to incorporate some of the coupling into the factors and to calculate spectra of molecules with more than
a dozen atoms. We use multi-dimensional factors that are eigenfunctions of reduced-dimension Hamiltonians. These can be
constructed, in different ways, by organizing the factors into a multiple layer tree. Each node in a layer of a tree represents
eigenfunctions of a reduced-dimension Hamiltonian for a group of coordinates. We have done calculations with tensor-train
and binary tree structures. Efficiency is significantly enhanced by representing the potential with the same tree structure. The
ideas are tested by computing energy levels of a 64-D model coupled oscillator Hamiltonian and of CH3CN (12 dimensions)
with a realistic potential.
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RG04
2:21 – 2:36
QUANTUM MONTE CARLO ALGORITHMS FOR DIAGRAMMATIC VIBRATIONAL STRUCTURE CALCULATIONS
MATTHEW HERMES, SO HIRATA, Department of Chemistry, University of Illinois at Urbana-Champaign,
Urbana, IL, USA.
Convergent hierarchies of theories for calculating many-body vibrational ground and excited-state wave functions, such
as Møller-Plesset perturbation theory or coupled cluster theory, tend to rely on matrix-algebraic manipulations of large, highdimensional arrays of anharmonic force constants, tasks which require large amounts of computer storage space and which are
very difficult to implement in a parallel-scalable fashion. On the other hand, existing quantum Monte Carlo (QMC) methods
for vibrational wave functions tend to lack robust techniques for obtaining excited-state energies, especially for large systems.
By exploiting analytical identities for matrix elements of position operators in a harmonic oscillator basis, we have developed
stochastic implementations of the size-extensive vibrational self-consistent field (MC-XVSCF) and size-extensive vibrational
Møller-Plesset second-order perturbation (MC-XVMP2) theories which do not require storing the potential energy surface
(PES). The programmable equations of MC-XVSCF and MC-XVMP2 take the form of a small number of high-dimensional
integrals evaluated using Metropolis Monte Carlo techniques. The associated integrands require independent evaluations
of only the value, not the derivatives, of the PES at many points, a task which is trivial to parallelize. However, unlike
existing vibrational QMC methods, MC-XVSCF and MC-XVMP2 can calculate anharmonic frequencies directly, rather
than as a small difference between two noisy total energies, and do not require user-selected coordinates or nodal surfaces.
MC-XVSCF and MC-XVMP2 can also directly sample the PES in a given approximation without analytical or grid-based
approximations, enabling us to quantify the errors induced by such approximations.
RG05
DIAGRAMMATIC VIBRATIONAL COUPLED-CLUSTER
2:38 – 2:53
JACOB A FAUCHEAUX, SO HIRATA, Department of Chemistry, University of Illinois at Urbana-Champaign,
Urbana, IL, USA.
A diagrammatic vibrational coupled-cluster method for calculation of zero-point energies and an equation-of-motion
coupled-cluster method for calculation of anharmonic vibrational frequencies are developed. The methods, which we refer
to as XVCC and EOM-XVCC respectively, rely on the size-extensive vibrational self-consistient field (XVSCF) method for
reference wave functions. The methods retain the efficiency advantages of XVSCF making them suitable for applications
to large molecules and solids, while they are numerically shown to accurately predict zero-point energies and frequencies of
small molecules as well. In particular, EOM-XVCC is shown to perform well for modes which undergo Fermi resonance
where traditional perturbative methods fail. Rules for the systematic generation and interpretation of the XVCC and EOMXVCC diagrams to any order are presented.
192
RG06
VIBRATIONAL JAHN-TELLER EFFECT IN NON-DEGENERATE ELECTRONIC STATES
2:55 – 3:10
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MAHESH B. DAWADI, BISHNU P THAPALIYA, Department of Chemistry, The University of Akron, Akron,
OH, USA; RAM BHATTA, Polymer Science, The University of Akron, Akron, OH, USA; DAVID S. PERRY,
Department of Chemistry, The University of Akron, Akron, OH, USA.
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The Jahn-Teller theorem a states that “All non-linear nuclear configurations are therefore unstable for an orbitally degenerate electronic state.” In 1982, Kellman b realized that the Jahn-Teller theorem also applies to nonlinear molecular species
in non-degenerate electronic states when there are high-frequency vibrations that are degenerate at a symmetrical reference
geometry. When those high frequencies can be considered as adiabatic functions of degenerate low-frequency coordinates,
there is a spontaneous Jahn-Teller distortion that lifts the degeneracy of the high-frequency vibrations. Kellman applied the
vibrational Jahn-Teller (vJT) concept to the Van der Waals dimer (SF6 )2 .
In this talk, the vJT concept is applied to E ⊗ e systems that are small bound molecules in non-degenerate electronic
states. The first case considered in systems for which the global minimum of the electronic potential has C3v symmetry.For
such systems, including (C6 H6 )Cr(CO)3 and CH3 CN, the vJT effect leads to a significant splitting of the degenerate highfrequency vibrations (CH or CO stretches), but the spontaneous vJT distortion is exceptionally small. The second case in
systems for which the global minimum of the electronic potential is substantially distorted from the C3v reference geometry.
For the second case systems, including CH3 OH and CH3 SH, the vJT splitting of the degenerate CH stretches is much larger,
on the order of several 10Äôs of cm−1 ). For both cases, there is the symmetry-required vibrational conical intersection at the
C3v reference geometry. For the second case systems, there are additional symmetry-allowed vibrational conical intersections
far from the C3v geometry but energetically accessible to the molecule at thermal energies. For both cases, the vibrationally
adiabatic surfaces, including the multiple conical intersections, are well described by modest extensions to a high-order
Hamiltonian that was developed for the electronic Jahn-Teller problem.c
a
b
c
H. A. Jahn, and E. Teller, Proc. R. Soc. Lond. A. 161, 220, (1937).
M. E. Kellman, Chem. Phys. Lett. 87, 171, (1982).
A. Viel, and W. Eisfeld, J. Chem. Phys. 120, 4603, (2004).
RG07
3:12 – 3:27
SPECTRAL SIGNATURES AND STRUCTURAL MOTIFS IN NEUTRAL AND PROTONATED HISTAMINE: A COMPUTATIONAL STUDY
SANTOSH KUMAR SRIVASTAVA, VIPIN BAHADUR SINGH, Department of Physics, Udai Pratap Autonomous College, Varanasi, India.
Histamine is an important neurotransmitter that acts as a chemical messenger to exhibit various functions in central and
peripheral tissues. The knowledge of its most favored forms is thus of great interest because its shape plays an important role
in the key-and-hole recognition process that occurs at the receptor sites. In the present work the conformational landscapes of
neutral and protonated histamine have been investigated by MP2 and DFT (employing the various density functionals M062X, B97X-D, B3LYP etc ) methods. The ground state geometry optimization of the four experimentally observed lowest
energy structures of the neutral histamine were performed at the MP2/aug-cc-pVDZ level of theory, for the first time. The
conformers 1G-IVa (A)1,2 and 3G-Ib (C)1,2 are predicted to be the most stable and the second most stable isolated structures
of the neutral histamine, respectively. Theoretical IR and Raman spectra of the above four conformers were investigated
and it was found that the alkyl CH stretch frequencies provides the most useful diagnostic of the ethylamine side chain
conformation and are most sensitive to conformational changes in histamine. The computed IR frequencies and intensities
of the experimentally observed most stable structure of protonated histamine are used to assign the observed vibrational
fundamentals. NH-stretching vibration in the vicinity of the amino group is predicted to be red shifted by 594 cm-1 due to the
strong intra-molecular hydrogen bonding (N-H...N). In the alkyl CH- stretching region the CH2(alpha) symmetric stretching
vibration attributed to the most intense IR band whereas the CH2(beta) symmetric stretching vibration belongs to the most
intense Raman band. The ring CC/CN stretch vibrational fundamental observed in the IRMPD spectra of histamineH+ is
found to be in remarkable agreement with the predicted frequency of 1597 cm-1 computed at B3LYP/6-311++G(2d,2p) level.
We investigated the low-lying excited states of each experimentally observed conformer of neutral histamine by means of
coupled cluster singles and approximate doubles (CC2) method and TDDFT methods and a satisfactory interpretation of the
electronic absorption spectra is obtained. 1. P. D. Godfrey and R. D. Brown, J. Am. Chem. Soc. 1998, 120, 10724-10732.
2. E. G. Robertson and J. P. Simons, Phys. Chem. Chem. Phys. 2001, 3, 1-18.
193
RG08
3:29 – 3:39
ANALOG OF DUSCHINSKY MATRIX AND CO-ASSIGNMENT OF FREQUENCIES IN DIFFERENT ELECTRONIC
STATES
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YURII PANCHENKO, ALEXANDER ABRAMENKOV, Department of Chemistry, Lomonosov Moscow State
University, Moscow, Russia.
The analog of the Duschinsky matrixa D is defined as D=(LI )−1 LII where LI and LII are the matrices of the vibrational
modes of the molecule under investigation. They are obtained by solving the vibrational problems in the I and II electronic
states, respectively. Choosing the dominant elements in columns of the D matrix and permuting these columns to arrange
these elements along the diagonal of the transformed matrix D* makes it possible to establish the correct co-assignment of the
calculated frequencies in the I and II electronic states. The rows of D* are for the vibrations in the I electronic state, whereas
the columns are for vibrations in the II electronic state. The results obtained may be tested by analogous calculations of D*
for isotopologues.
a
F. Duschinsky, Acta Physicochim. URSS, 7 (4), 551-566 (1937).
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Intermission
RG09
HIGH RESOLUTION INFRARED SPECTRA OF TRIACETYLENE
3:58 – 4:13
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KIRSTIN D DONEY, DONGFENG ZHAO, HAROLD LINNARTZ, Leiden Observatory, Sackler Laboratory
for Astrophysics, Universiteit Leiden, Leiden, Netherlands.
Triacetylene, HC6 H, is the longest poly-acetylene chain found in space, and is believed to be involved in the formation
of longer chain molecules and polycyclic aromatic hydrocarbons (PAHs). However, abundances are expected to be low, and
observational confirmation requires knowledge of the gas-phase spectra, which up to now has been incomplete with only the
weak, low lying bending modes being known. We present new infrared (IR) spectra in the C-H stretch region obtained using
ultra-sensitive and highly precise IR continuous wave cavity ring-down spectroscopy (cw-CRDS), combined with supersonic
plasma expansionsa . The talk reviews the accurate determination of the rotational constants of the asymmetric fundamental
mode, ν5 , including discussion on the perturber state, and associated hot bandsb . The determined molecular parameters
are accurate enough to aid astronomical searches with such facilities as ALMA (Atacama Large Millimeter Array) or the
upcoming JWST (James Webb Space Telecscope), which can now probe even trace molecules (abundances of ∼ 10−6 10−10 with respect to H2 ).
a
b
D. Zhao, J. Guss, A. Walsh, H. Linnartz, Chem. Phys. Lett., 565, 132 (2013)
K.D. Doney, D. Zhao, H. Linnartz, in preparation
RG10
4:15 – 4:30
INFRARED AND ULTRAVIOLET SPECTROSCOPY OF GAS-PHASE IMIDAZOLIUM AND PYRIDINIUM IONIC
LIQUIDS.
JUSTIN W. YOUNG, RYAN S BOOTH, CHRISTOPHER ANNESLEY, JAIME A. STEARNS, Space Vehicles
Directorate, Air Force Research Lab, Kirtland AFB, NM, USA.
Ionic liquids (ILs) are a highly variable and potentially game-changing class of molecules for a number of Air Force
applications such as satellite propulsion, but the complex nature of IL structure and intermolecular interactions makes it difficult to adequately predict structure-property relationships in order to make new IL-based technology a reality. For example,
methylation of imidazolium ionic liquids leads to a substantial increase in viscosity but the underlying physical mechanism is
not understood. In addition, the role of hydrogen bonding in ILs, and especially its relationship to macroscopic properties, is
a matter of ongoing research. Here we describe the gas-phase spectroscopy of a series of imidazolium- and pyridinium-based
ILs, using a combination of infrared spectroscopy and density functional theory to establish the intermolecular interactions
present in various ILs, to assess how well they are described by theory, and to relate microscopic structure to macroscopic
properties.
194
RG11
4:32 – 4:47
GROUND AND EXCITED STATE ALKYL CH STRETCH IR SPECTRA OF STRAIGHT-CHAIN ALKYLBENZENES
DANIEL M. HEWETT, JOSEPH A. KORN, TIMOTHY S. ZWIER, Department of Chemistry, Purdue University, West Lafayette, IN, USA.
RG12
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Vibrational spectra of alkanes in the CH stretch region are often complicated by Fermi resonance with the overtone
of the CH bends. This complication has made the CH stretch region difficult to use as a spectroscopic tool for assigning
structures to experimental infrared spectra. A first-principles model accounting for Fermi resonance has been developed
by Sibert and co-workers, and has been successfully implemented to predict the CH stretch region of alkyl groups in a
variety of settings (both -CH2 - and -CH3 ). We have recorded jet-cooled, single-conformation infrared spectra of a series
of straight chain alkylbenzenes having chain lengths of two carbons and longer, serving as a foundation for further tests
and refinement of the theoretical model. Ground and excited state IR spectra of these alkylbenzenes were acquired using
fluorescence dip infrared spectroscopy. A novel approach for taking the excited state spectra that utilizes the gain of a second,
infrared-induced fluorescence peak will be discussed and compared to the typical depletion spectra, using ethylbenzene as a
prototypical system.
4:49 – 5:04
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ASYMMETRY OF M+ (H2 O)RG COMPLEXES, (M=V, Nb) REVEALED WITH INFRARED SPECTROSCOPY
TIMOTHY B WARD, Department of Chemistry, University of Georgia, Athens, GA, USA; EVANGELOS MILIORDOS, SOTIRIS XANTHEAS, Physical Sciences Division, Pacific Northwest National Laboratory, Richland,
WA, USA; MICHAEL A DUNCAN, Department of Chemistry, University of Georgia, Athens, GA, USA.
M+ (H2 O)Ar and M+ (H2 O)Ne clusters (M=V, Nb) were produced in a laser vaporization/pulsed nozzle source. The clusters were then mass selected in a time-of-flight mass spectrometer and studied with infrared photodissociation spectroscopy
in the OH stretching region. Spectra showed two bands, with the asymmetric band showing k-type rotational structure. Previous work has shown that most metal-water rare gas-tagged systems adopt C2v geometry and exhibit the well-known 3:1
ortho:para ratio in the k-type rotational structure in asymmetric stretch band. However these two metals display a pattern that
indicates a breaking of the C2v symmetry. Computational work confirms the breaking of C2v symmetry giving an Ar-M+ -O
angle of 163.7 degrees for V and 172.1 degrees for Nb. In the ground state we obtain rotational constants that match up well
with obtained spectra using 166 degrees for V and 175 degrees for Nb.
RG13
5:06 – 5:21
INFRARED SPECTROSCOPY OF PROTONATED ACETYLACETONE AND MIXED ACETYLACETONE/WATER
CLUSTERS
DANIEL MAUNEY, JON MANER, Department of Chemistry, University of Georgia, Athens, GA, USA; DAVID
C McDONALD, Chemistry, University of Georgia, Athens, GA, USA; MICHAEL A DUNCAN, Department of
Chemistry, University of Georgia, Athens, GA, USA.
Acetylacetone (acac) is the simplest of the beta-diketones. which have both keto and enol tautomers with multiple
protonation sites. We readily produce the protonated forms in the gas phase and the current investigation uses vibrational
spectroscopy coupled with argon tagging to determine which protonated isomers are present in clusters of acac and the effects
of solvation on the isomers observed.
195
RG14
HEAVY ATOM VIBRATIONAL MODES AND LOW-ENERGY VIBRATIONAL AUTODETACHMENT IN
NITROMETHANE ANIONS
5:23 – 5:38
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MICHAEL C THOMPSON, JILA and the Department of Chemistry and Biochemistry, University of ColoradoBoulder, Boulder, CO, USA; JOSHUA H BARABAN, Department of Chemistry, University of Colorado, Boulder, CO, USA; JOHN F. STANTON, Department of Chemistry, The University of Texas, Austin, TX, USA;
J. MATHIAS WEBER, JILA and the Department of Chemistry and Biochemistry, University of ColoradoBoulder, Boulder, CO, USA.
We use Ar predissociation and vibrational autodetachment below 2100 cm−1 to obtain vibrational spectra of the lowenergy modes of nitromethane anion. We interpret the spectra using anharmonic calculations, which reveal strong mode
coupling and Fermi resonances. Not surprisingly, the number of evaporated Ar atoms varies with photon energy, and we
follow the propensity of evaporating two versus one Ar atoms as photon energy increases. The photodetachment spectrum is
discussed in the context of threshold effects and the importance of hot bands.
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RG15
5:40 – 5:55
OBSERVATION OF DIPOLE-BOUND STATE AND HIGH-RESOLUTION PHOTOELECTRON IMAGING OF COLD
ACETATE ANIONS
GUO-ZHU ZHU, DAO-LING HUANG, LAI-SHENG WANG, Department of Chemistry, Brown University,
Providence, RI, USA.
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We report the observation of a dipole-bound state and a high-resolution photoelectron imaging study of cryogenically
cooled acetate anions (CH3 COO− ). Both high-resolution non-resonant and resonant photoelectron spectra via the dipolebound state of CH3 COO− are obtained. The binding energy of the dipole-bound state relative to the detachment threshold
is determined to be 53 ±8 cm−1 . The electron affinity of the CH3 COO• neutral radical is measured accurately as 26 236
±8 cm−1 (3.2528 ±0.0010 eV) using high-resolution photoelectron imaging. This accurate electron affinity is validated by
observation of autodetachment from two vibrational levels of the dipole-bound state of CH3 COO− . Excitation spectra to
the dipole-bound states yield rotational profiles, allowing the rotational temperature of the trapped CH3 COO− anions to be
evaluated 1 .
[1] D. L. Huang, G. Z. Zhu and L. S. Wang, J .Chem.Phys., 2015, 142, 091103
196
RH. Clusters/Complexes
Chair: Galen Sedo, University of Virginia’s College at Wise, Wise, VA, USA
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RH01
1:30 – 1:45
CHIRPED PULSE AND CAVITY FT MICROWAVE SPECTROSCOPY OF THE HCCH-2,6-DIFLUOROPYRIDINE
WEAKLY BOUND COMPLEX
CHRIS DEWBERRY, BECCA MACKENZIE, KEN LEOPOLD, Chemistry Department, University of Minnesota, Minneapolis, MN, USA.
RH02
in
The microwave spectrum of the HCCH-2,6-difluoropyrine complex has been observed using a chirped pulse and conventional cavity-type Fourier transform microwave spectroscopy. The acetylene moiety forms a hydrogen bond to the nitrogen
of the 2,6-difluoropyridine, and this structure is contrasted with several systems involving HCCH or CO2 bound to pyridine
or 2,6-difluoropyridine. The results of DFT calculations support the experimental observations and are reported as well. The
chirped pulse spectrometer is new in our laboratory and is built in tandem with our cavity-type spectrometer with a design
that allows for switching between the two modes of operation without having to break vacuum. Pertinent details of the
spectrometer will also be given.
1:47 – 1:57
Xe QUADRUPOLE COUPLING CONSTANT
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MICROWAVE SPECTRUM, VAN DER WAALS BOND LENGTH, AND
OF Xe-SO3
131
CHRIS DEWBERRY, Chemistry Department, University of Minnesota, Minneapolis, MN, USA; ANNA HUFF,
Chemistry Deparment, Gustavus Adolphus College, St. Peter, MN, USA; BECCA MACKENZIE, KEN
LEOPOLD, Chemistry Department, University of Minnesota, Minneapolis, MN, USA.
Nine isotopologues of Xe-SO3 have been observed by pulsed-nozzle Fourier transform microwave spectroscopy. The
complex is a symmetric top with a Xe-S van der Waals distance of 3.577(2) Å. The increase in rare gas distance relative to
that in Kr-SO3 is equal to the difference in van der Waals radii between Xe and Kr. The 131 Xe nuclear quadrupole coupling
constant indicates that the electric field gradient at the xenon nucleus is 78% larger than that at the Kr nucleus in Kr-SO3 .
RH03
1:59 – 2:14
DIMETHYL SULFIDE-DIMETHYL ETHER AND ETHYLENE OXIDE-ETHYLENE SULFIDE COMPLEXES INVESTIGATED BY FOURIER TRANSFORM MICROWAVE SPECTROSCOPY AND AB INITIO CALCULATION
YOSHIYUKI KAWASHIMA, YOSHIO TATAMITANI, TAKAYUKI MASE, Applied Chemistry, Kanagawa Institute of Technology, Atsugi, Japan; EIZI HIROTA, The Central Office, The Graduate University for Advanced
Studies, Hayama, Kanagawa, Japan.
The ground-state rotational spectra of the dimethyl sulfide-dimethyl ether (DMS-DME) and the ethylene oxide and
ethylene sulfide (EO-ES) complexes were observed by Fourier transform microwave spectroscopy, and a-type and c-type
transitions were assigned for the normal, 34 S, and three 13 C species of the DMS-DME and a-type and b-type rotational
transitions for the normal, 34 S, and two 13 C species of the EO-ES. The observed transitions were analyzed by using an
S-reduced asymmetric-top rotational Hamiltonian. The rotational parameters thus derived for the DMS-DME were found
consistent with a structure of Cs symmetry with the DMS bound to the DME by two C-H(DMS)—O and one S—H-C(DME)
hydrogen bonds. The barrier height V 3 to internal rotation of the ”free” methyl group in the DME was determined to be 915.4
(23) cm−1 , which is smaller than that of the DME monomer, 951.72 (70) cm−1 ,a and larger than that of the DME dimer,
785.4 (52) cm−1 .b For the EO-ES complex the observed data were interpreted in the terms of an antiparallel Cs geometry
with the EO bound to the ES by two C-H(ES)—O and two S—H-C(EO) hydrogen bonds. We have applied a natural bond
orbital (NBO) analysis to the DMS-DME and EO-ES to calculate the stabilization energy CT (= ∆Eσσ*), which were closely
correlated with the binding energy EB , as found for other related complexes.
a
b
Y. Niide and M. Hayashi, J. Mol. Spectrosc. 220, 65-79 (2003).
Y. Tatamitani, B. Liu, J. Shimada, T. Ogata, P. Ottaviani, A. Maris, W. Caminati, and J. L. Alonso, J. Am. Chem. Soc. 124, 2739-2743 (2002).
197
RH04
INTERNAL DYNAMICS IN SF6 ···NH3 OBSERVED BY BROADBAND ROTATIONAL SPECTROSCOPY
2:16 – 2:31
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DROR M. BITTNER, DANIEL P. ZALESKI, SUSANNA L. STEPHENS, NICK WALKER, School of Chemistry, Newcastle University, Newcastle-upon-Tyne, United Kingdom; ANTHONY LEGON, School of Chemistry,
University of Bristol, Bristol, United Kingdom.
in
The rotational spectra of SF6 ···NH3 isotopologues have been observed in a pulsed nozzle chirped pulse Fourier-transform
microwave spectrometer in the frequency range 6.5-18.5 GHz. The spectrum of SF6 ···14 NH3 has been fitted to a Hamiltonian
describing a symmetric top complex in which two symmetric top subunits undergo free internal rotation about a common
symmetry axis. The distance between the centers of mass of the two monomers was found to be 4.15776(7) Å. Challenges associated with fitting |m|=1 transitions (correlating with K of free NH3 ) for SF6 ···14 ND3 imply complicated internal dynamics
occurs within the complex.
RH05
2:33 – 2:48
EVIDENCE FOR A COMPLEX BETWEEN THF AND ACETIC ACID FROM BROADBAND ROTATIONAL SPECTROSCOPY
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DANIEL P. ZALESKI, DROR M. BITTNER, JOHN CONNOR MULLANEY, SUSANNA L. STEPHENS,
School of Chemistry, Newcastle University, Newcastle-upon-Tyne, United Kingdom; ADRIAN KING,
MATTHEW HABGOOD, Sensors and Spectroscopy, Atomic Weapons Establishment, Aldermaston, United
Kingdom; NICK WALKER, School of Chemistry, Newcastle University, Newcastle-upon-Tyne, United Kingdom.
Evidence for a complex between tetrahydrofuran (THF) and acetic acid from broadband rotational spectroscopy will be
presented. Transitions believed to belong to the complex were first identified in a gas mixture containing small amounts of
THF, triethyl borane, and acetic acid balanced in argon. Ab initio calculations suggest a complex between THF and acetic acid
is more likely to form compared to the analogous acetic acid complex with triethyl borane, the initial target. The observed
rotational constants are also more similar to those predicted for a complex formed between THF and acetic acid, than for those
of a complex formed between triethyl borane and acetic acid. Subsequently, multiple isotopologues of acetic acid have been
measured, confirming its presence in the structure. No information has yet been obtained through isotopic substitution within
the THF sub-unit. Ab initio calculations predict the most likely structure is one where the acetic acid subunit coordinates over
the ring creating a ”bridge” between the THF oxygen, the carboxylic O-H, and the carbonyl oxygen to a hydrogen atom on
the back of the ring.
RH06
THE ROTATIONAL SPECTRUM OF PYRIDINE-FORMIC ACID
2:50 – 3:00
LORENZO SPADA, QIAN GOU, Dep. Chemistry ’Giacomo Ciamician’, University of Bologna, Bologna,
Italy; BARBARA MICHELA GIULIANO, Department of Chemistry, University of Bologna, Bologna, Italy;
WALTHER CAMINATI, Dep. Chemistry ’Giacomo Ciamician’, University of Bologna, Bologna, Italy.
The rotational spectrum of three 1:1 complexes of pyridine with formic acid has been observed and assigned using pulsed
jet Fourier transform microwave technique. The two subunits are held together through one O-H···N hydrogen bond and one
C-H···O weak hydrogen bond, forming a seven-membering cyclic structure. The rotational spectrum of the pyridine-HCOOD
isotopologue is considerably shifted towards lower frequencies, with respect to the ”rigid” model, suggesting a considerable
Ubbelohde effect, similar in nature to that observed in the bi-molecules of carboxylic acids.
Intermission
198
RH07
3:19 – 3:34
FOURIER-TRANSFORM MICROWAVE AND MILLIMETERWAVE SPECTROSCOPY OF THE H2 -HCN MOLECULAR
COMPLEX
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KEIICHI TANAKA, KENSUKE HARADA, Department of Chemistry, Kyushu University, Fukuoka, Japan;
YOSHIHIRO SUMIYOSHI, Division of Pure and Applied Science, Faculty of Science and Technology, Gunma
University, Maebashi, Japan; MASAKAZU NAKAJIMA, YASUKI ENDO, Department of Basic Science, The
University of Tokyo, Tokyo, Japan.
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Fourier-Transform microwave (FTMW) spectroscopy has been applied to observe the J = 1 - 0 rotational transitions of
the H2 -HCN/DCN complexes containing both the para-H2 (IH2 =0) and ortho-H2 (IH2 =1) moleculea . Rotational spectra of
H2 -HCN/DCN up to J = 5 - 4 were also observed in the millimeter-wave (MMW) region below 180 GHzb . Observed FTMW
lines for H2 -HCN/DCN split into hyperfine components due to the nuclear quadrupole interaction of N and D nuclei. For
the ortho-H2 species, the hyperfine splitting due to the magnetic interaction between the hydrogen nuclear spin of ortho-H2
part (jH2 =1, IH2 =1) was also observed, but not for the para-H2 species (jH2 =0, IH2 =0). From the observed nuclear spinspin coupling constants of ortho-H2 species, d = 21.90(47) and 24.66(68) kHz for HCN and DCN complexes, respectively,
the average values of < P2 (cosθ) > = 0.380(8) and 0.439(10) were derived indicating the nearly free rotation of H2 in the
complex with jH2 = 1 and kH2 = 0.
The nuclear quadrupole interaction constants due to N and D nuclei show that the HCN/DCN part executes a floppy
motion with a large mean square amplitude of about 29/25 and 33/30 degree in the para and ortho species, respectively. From
the observed rotational constants, the center-of-mass distances of H2 and HCN/DCN were derived to be 3.9617(5)/4.00356
(43) Å for the ortho species and 4.1589(13)/4.1596 (36) Å for the para species. The isotope effect on rotational constants
confirmed the totally different configurations in the ortho and para species: H2 is attached to the H/D end of HCN/DCN for
the para species, while to the N end for the ortho species, as suggested by IR spectroscopy and theoretical study.
a
b
M. Ishiguro et al., Chem. Phys. Lett. 554, 33 (2012).
M. Ishiguro et al., J. Chem. Phys. 115, 5155 (2001).
RH08
MICROWAVE SPECTROSCOPY OF THE CYCLOPENTANOL - WATER DIMER
3:36 – 3:51
BRANDON CARROLL, IAN A FINNERAN, GEOFFREY BLAKE, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA.
Observations of gas-phase dimers are one of the simplest methods for studying bimolecular interactions. These dimers
are excellent model systems for molecular interactions, providing a benchmark for theoretical studies, and a basis for understanding and modeling more complex interactions. Of particular interest are studies of strong (O—H· · · O—H) and
weak (C—H· · · O—H) long-range interactions of water. We have recently recorded the pure rotational spectrum of the
cyclopentanol-water dimer with chirped-pulse Fourier transform microwave spectroscopy (CP-FTMW). We will present the
spectrum of this dimer and discuss its structure in the context of C—H· · · O—H and O—H· · · O—H bonding.
RH09
HYDROGEN-BONDING AND HYDROPHOBIC INTERACTIONS IN THE ETHANOL-WATER DIMER
3:53 – 4:08
IAN A FINNERAN, BRANDON CARROLL, MARCO A. ALLODI, GEOFFREY BLAKE, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA.
The conformational energy landscape of the ethanol-water dimer is determined by the relative hydrogen-bond donor and
acceptor strengths of the two molecules, as well as weaker hydrophobic interactions between the water and the ethyl group.
Using a combination of ab initio calculations and chirped-pulse Fourier transform microwave spectroscopy, we have recorded
the first rotationally-resolved, jet-cooled spectrum of the ethanol-water dimer between 8-18.5 GHz and identified two waterdonor ethanol-acceptor conformers. The lowest energy conformer is chiral, has ethanol in the gauche configuration, and is
consistent with previous raman and infrared results.a The second conformer corresponds to the trans-ethanol configuration,
and exhibits a significant splitting.
a
Nedić, Marija, et al. PCCP 13.31 (2011): 14050-14063.
199
RH10
4:10 – 4:25
THE INFLUENCE OF FLUORINATION ON STRUCTURE OF THE TRIFLUOROACETONITRILE WATER COMPLEX
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WEI LIN, Department of Chemistry, University of Texas, Brownsville, TX, USA; ANAN WU, XIN LU, Department of Chemistry, Xiamen University, Xiamen, China; DANIEL A. OBENCHAIN, STEWART E. NOVICK,
Department of Chemistry, Wesleyan University, Middletown, CT, USA.
Acetonitrile, CH3 CN, and trifluoroacetonitrile, CF3 CN, are symmetric tops. In a recent study of the rotational
spectrum of the acetonitrile and water complex, it was observed that the structure was also an effective symmetric
topa , with the external hydrogen freely rotating about the O − H bond aligned towards the nitrogen of the cyanide of
CH3 CN. Unlike the CH3 CN − H2 O complex, the CH3 CN − Ar and CF3 CN − Ar complexes were observed to be
asymmetric tops. Having a series of symmetric and asymmetric top complexes of acetonitrile and trifluoracetonitrile for
comparison, we report the rotational spectrum of the weakly bound complex between trifluoroacetonitrile and water. Rotational constants and quadrupole coupling constants will be presented, and the structure of CF3 CN − H2 O will be revealed.
SPOILER ALERT: It’s an asymmetric top.
Lovas, F.J.; Sobhanadri, J. Microwave rotational spectral study of CH3 CN − H2 O and Ar − CH3 CN. J. Mol. Spetrosc. 2015, 307, 59-64.
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a
RH11
4:27 – 4:42
THE POSITION OF DEUTERIUM IN THE HOD − N2 O AS DETERMINED BY STRUCTURAL AND NUCLEAR
QUADRUPOLE COUPLING CONSTANTS
DANIEL A. OBENCHAIN, DEREK S. FRANK, STEWART E. NOVICK, Department of Chemistry, Wesleyan
University, Middletown, CT, USA; WILLIAM KLEMPERER, Department of Chemistry and Chemical Biology,
Harvard University, Cambridge, MA, USA.
A recent investigation of the HOD − N2 O complex measuring the OH + OD excited band in the near-IR was completed
by Foldes et al.a During this study, one of us (WAK) was contacted about the position of deuterium in the HOD − N2 O
complex, as his group completed the original microwave study of H2 O − N2 O and its deuterated isotopologuesb in 1992. The
results of this microwave study did not give the orientation of HOD in the complex, however, we present here a supplementary
study to the original microwave work using a Balle-Flygare cavity instrument, attempting to determine the orientation of
HOD relative to the N2 O. In addition to a Kraitchman and a least-squares inertial structure fit of the molecule, we present
the nuclear quadrupole coupling tensor of deuterium to determine the position of HOD in the complex.
a
Földes, T; Lauzin, C.; Vanfleteren, T.; Herman, M.; Lièvin, J.; Didriche. K. High-resolution, near-infrared CW-CRDS and ab initio investigations of N2 O − HDO.Mol.
Phys. 2015, 113(5),473-482.
b
Zolandz, D.; Yaron, D.; Peterson, K.I.; Klemperer, W. Water in weak interactions: The structure of the water-nitrous oxide complex. J. Chem. Phys. 1992, 97,2861.
200
RH12
4:44 – 4:59
THE CP-FTMW SPECTROSCOPY AND ASSIGNMENT OF THE MONO- AND DIHYDRATE COMPLEXES OF PERFLUOROPROPIONIC ACID
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G. S. GRUBBS II, Department of Chemistry, Missouri University of Science and Technology, Rolla, MO, USA;
DANIEL A. OBENCHAIN, DEREK S. FRANK, STEWART E. NOVICK, Department of Chemistry, Wesleyan
University, Middletown, CT, USA; S. A. COOKE, Natural and Social Science, Purchase College SUNY, Purchase,
NY, USA; AGAPITO SERRATO III, WEI LIN, Department of Chemistry, University of Texas, Brownsville, TX,
USA.
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While searching for the chirped pulse spectra of allyl phenyl ether, the authors used
current rotational spectroscopic fitting tools to assign multiple sets of spectra of unknown
origin. Previous chirped pulse experiments searching for hydrate complexes of perfluoropropionic acid had not been successful but, through theoretical agreement, it was determined that at least one of the sets of unknown spectra observed belonged to the perfluoropropionic acid-water complex. Further determination showed that the dihydrate had
also been observed. The determination process and spectral assignment will be discussed.
Structural determinations of the complexes will also be discussed.
RH13
5:01 – 5:16
HYDROGEN BONDING IN 4-AMINOPHENYL ETHANOL: A COMBINED IR-UV DOUBLE RESONANCE AND MICROWAVE STUDY
CAITLIN BRAY, CARA RAE RIVERA, E. A. ARSENAULT, DANIEL A. OBENCHAIN, STEWART E.
NOVICK, JOSEPH L. KNEE, Department of Chemistry, Wesleyan University, Middletown, CT, USA.
Both amine and hydroxyl functional groups are present in
4-aminophenyl ethanol (4-AE), and each functional group can
form hydrogen bonds with carboxylic acids, such as formic acid
and acetic acid.
Predicting the structures of such complexes
involving 4-AE is rather complex, given the many possible conformations and their similar (and method and basis-dependent)
energies. In particular, the carboxyl group, -COOH, can act as
both as a hydrogen bond donor or acceptor, or both at once.
OH
H2N
In this study we report the formic acid − 4-AE hydrogen bonded complex. An infrared-ultraviolet double resonance
spectrometer is used to examine the shifts in IR frequencies of 4-AE from the monomer to the complex. Fourier transform
microwave spectroscopy is used to determine structures of the species. Results from both experiments are compared to DFT
and ab initio results. Time permitting, results of the water complex with 4-AE will also be presented.
201
RH14
5:18 – 5:28
THEORETICAL STUDY OF THE EFFECT OF DOPING CLUSTERS (ZNO) 6 BY THE SELENIUM USING THE DFT
NOUR EL HOUDA BENSIRADJ, OURIDA OUAMERALI, Laboratory lctcp, University USTHB, Algiers, Algeria.
in
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Nano structures (ZnO) 6 have a great interest in the creation of new materials used in energy technologies. We have used
the technique of doping ie introducing impurities at the geometry of these clusters; replacing each time by an oxygen atom a
selenium atom. This implies a change in the electronic and energetic properties. Clusters obtained (containing selenium) have
interesting characteristics in the development of solar energy systems and the field of radiology in medicine. The clusters
studied are shown in a 3D geometry (crystal form b) .The geometric parameters of these systems are calculated using the
theory of density functional (DFT) . The optimisation the first excited state is performed at the Hartree-Fock method, Single
Configuration interaction (HF / CIS), the transmission-absorption spectra are given by the TDDFT method. The results for
the excited states have a good process for materials for application in solar cells. The emission spectra of these clusters are
located in the tera-hertz region (between the far infrared and microwave), which is less than the ionizing X-ray spectral region
and could soon replace for applications medicine.
RH15
BORONYL MIMICS GOLD: A PHOTOELECTRON SPECTROSCOPY STUDY
5:30 – 5:45
TIAN JIAN, GARY LOPEZ, LAI-SHENG WANG, Department of Chemistry, Brown University, Providence,
RI, USA.
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Previous studies have found that gold atom and boronyl bear similarities in bonding in many gas phase clusters.a b c d
B10 (BO), B12 (BO), B3 (BO)n (n=1, 2) were found to possess similar bonding and structures to B10 Au, B12 Au, B3 Aun (n=1,
2), respectively. During the recent photoelectron spectroscopy experiments, the spectra of BiBO− and BiAu− clusters are
found to exhibit similar patterns, hinting that they possess similar geometric structures. While BiAu− is a linear molecule,
BiBO− is also linear. The similarity in bonding between BiBO− and BiAu− is owing to the fact that Au and BO are
monovalent σ ligands. The electron affinities are measured to be 1.79±0.04eV for BiBO− and 1.36±0.02eV for BiAu− . The
current results provide new examples for the BO/Au isolobal analogy and enrich the chemistry of boronyl and gold.
a
H.-J. Zhai, C.-Q. Miao, S.-D. Li, L.-S. Wang, J. Phys. Chem. A 2010, 114, 12155–1216
Q. Chen, H. Bai, H.-J. Zhai, S.-D. Li, L.-S. Wang, J. Chem. Phys. 2013, 139, 044308
H. Bai, H.-J. Zhai, S.-D. Li, L.-S. Wang, Phys. Chem. Chem. Phys., 2013, 15, 9646–9653
d
H.-J. Zhai, Q. Chen, H. Bai, S.-D. Li, L.-S. Wang, Acc. Chem. Res. 2014, 47, 2435-2445
b
c
202
RI. Astronomy
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Chair: Harshal Gupta, California Institute of Technology, Pasadena, CA, USA
RI01
1:30 – 1:45
THE COMPLETE, TEMPERATURE RESOLVED SPECTRUM OF METHYL FORMATE BETWEEN 214 AND 265 GHZ
JAMES P. McMILLAN, SARAH FORTMAN, CHRISTOPHER F. NEESE, FRANK C. DE LUCIA, Department
of Physics, The Ohio State University, Columbus, OH, USA.
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We have studied methyl formate, one of the so-called ‘astronomical weeds’, in the 214–265 GHz band. We have experimentally gathered a set of intensity calibrated, complete, and temperature resolved spectra from across the astronomically
significant temperature range of 248–406 K. Using our previously reported method of analysisa , the point by point method,
we are capable of generating the complete spectrum at an arbitrary temperature. Thousands of lines, of nontrivial intensity,
which were previously not included in the available astrophysical catalogs have been found.
The sensitivity of the point by point analysis is such that we are able to identify lines which would not have manifest in a
single scan across the band. The consequence has been to reveal not only a number of new methyl formate lines, but also trace
amounts of contaminants. We show how the intensities from the contaminants can be removed with indiscernible impact on
the signal from methyl formate. To do this we use the point by point results from our previous studies of these contaminants.
The efficacy of this process serves as strong proof of concept for usage of our point by point results on the problem of the
‘weeds’. The success of this approach for dealing with the weeds has also previously been reported.b
a
b
J. McMillan, S. Fortman, C. Neese, F. DeLucia, ApJ. 795, 56 (2014)
S. Fortman, J. McMillan, C. Neese, S. Randall, and A. Remijan, J. Mol. Spectrosc. 280, 11 (2012).
RI02
ROTATIONAL SPECTROSCOPY OF 4-HYDROXY-2-BUTYNENITRILE
1:47 – 2:02
R. A. MOTIYENKO, L. MARGULÈS, Laboratoire PhLAM, UMR 8523 CNRS - Université Lille 1, Villeneuve
d’Ascq, France; J.-C. GUILLEMIN, Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS - Université
de Rennes 1, Rennes, France.
Recently we studied the rotational spectrum of hydroxyacetonitrile (HOCH2 CN, HAN) in order to provide a firm basis
for its possible detection in the interstellar mediuma . Different plausible pathways of the formation of HAN in the interstellar
conditions were proposed;b however, up to now, the searches for this molecule were unsuccessful. To continue the study of
nitriles that represent an astrophysical interest we present in this talk the analysis of the rotational spectrum of 4-hydroxy-2butynenitrile (HOCH2 CC-CN, HBN), the next molecule in the series of hydroxymethyl nitriles. Using the Lille spectrometer
the spectrum of HBN was measured in the frequency range 50 – 500 GHz. From the spectroscopic point of view HBN
molecule is rather similar to HAN, because of -OH group tunnelling in gauche conformation. As it was previously observed
for HAN, due to this large amplitude motion, the splittings in the rotational spectra of HBN are easily resolved making the
spectral analysis more difficult. Additional difficulties arise from the near symmetric top character of HBN (κ = −0.996), and
very dense spectrum because of relatively small values of rotational constants and a number of low-lying excited vibrational
states. The analysis carried out in the frame of reduced axis system approach of Pickettc allows to fit within experimental
accuracy all the rotational transitions in the ground vibrational state. Thus, the results of the present study provide a reliable
catalog of frequency predictions for HBN.
The support of the Action sur Projets de l’INSU PCMI, and ANR-13-BS05-0008-02 IMOLABS is gratefully acknowledged
a
Margulès L., Motiyenko R.A., Guillemin J.-C. 68th ISMS, 2013, TI12.
Danger G. et al. Phys. Chem. Chem. Phys. 2014, 16, 3360.
c
Pickett H.M. J. Chem. Phys. 1972, 56, 1715.
b
203
RI03
TIME-DOMAIN TERAHERTZ SPECTROSCOPY OF ISOLATED PAHS
2:04 – 2:19
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BRANDON CARROLL, MARCO A. ALLODI, Division of Chemistry and Chemical Engineering, California
Institute of Technology, Pasadena, CA, USA; BRETT A. McGUIRE, NAASC, National Radio Astronomy Observatory, Charlottesville, VA, USA; SERGIO IOPPOLO, Department of Physical Sciences, The Open University,
Milton Keynes, UK; GEOFFREY BLAKE, Division of Chemistry and Chemical Engineering, California Institute
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Polycyclic aromatic hydrocarbons (PAHs) are a strong candidate as carriers of the unidentified infrared features (UIRs).
As UIR carriers, PAHs may account for up to 20% of the interstellar carbon budget and may play key roles in many chemical
and physical processes in the ISM. Laboratory and astronomical observations in the TeraHertz (THz) regime offer a unique
method to study these species through observations of low frequency vibrational modes of individual molecules as well as
bulk phonon modes. Embedding PAHs in matrices enables the differentiation of bulk and single-molecule modes, as well
as the investigation of the interaction between PAHs and both polar and apolar matrices. Such work provides a basis for
further studies of the effects of PAHs on interstellar ices. We will present the THz time-domain spectra (0.3 - 7 THz) of
PAHs embedded in N2 and H2 O matrices, and discuss the importance of these spectra for future laboratory and astronomical
studies.
RI04
2:21 – 2:36
HIGH-RESOLUTION IR ABSORPTION SPECTROSCOPY OF POLYCYCLIC AROMATIC HYDROCARBONS: SHINING LIGHT ON THE INTERSTELLAR 3 MICRON EMISSION BANDS
ELENA MALTSEVA, Van’ t Hoff Institute for Molecular Sciences, University of Amsterdam, Amsterdam,
Netherlands; ALESSANDRA CANDIAN, XANDER TIELENS, Leiden Observatory, University of Leiden, Leiden, Netherlands; ANNEMIEKE PETRIGNANI, J. OOMENS, Institute for Molecules and Materials (IMM),
Radboud University Nijmegen, Nijmegen, Netherlands; WYBREN JAN BUMA, Van’ t Hoff Institute for Molecular Sciences, University of Amsterdam, Amsterdam, Netherlands.
Various astronomical objects show distinctive series of IR emission bands indicated as unidentified infrared emission
bands. These features are nowadays mainly attributed to the IR fluorescence of Polycyclic Aromatic Hydrocarbons (PAHs)
even though an unambiguous identification of which PAHs are involved has not been possible yet. We present here a highresolution IR absorption study of a number of jet-cooled polycyclic aromatic hydrocarbons in the 3.3 µm region obtained
by IR-UV ion depletion techniques. The experimental spectra display many more bands than expected, and lead to the
conclusion that the appearance of the spectrum is dominated by fourth-order vibrational coupling terms. This has far-reaching
consequences since up till now the assignment of infrared emission features observed in different types of space objects in
this wavelength region -and the conclusions drawn from these assignments on the evolution of interstellar gas- has relied
heavily on harmonic quantum chemical calculations. We also observe that the presence of bay-hydrogen sites in a PAH leads
to a shift of the overall spectrum to the high-energy side and to a broadening of the 3 µm band. This observation provides
an appealing explanation for previous speculations that the emission of 3 µm band consists of two components. Moreover, it
paves for using this structure to derive the composition of different objects.
204
RI05
2:38 – 2:53
EXPLORING MOLECULAR COMPLEXITY WITH ALMA (EMoCA): HIGH-ANGULAR-RESOLUTION OBSERVATIONS OF SAGITTARIUS B2(N) AT 3 mm
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HOLGER S. P. MÜLLER, I. Physikalisches Institut, Universität zu Köln, Köln, Germany; ARNAUD BELLOCHE, KARL M. MENTEN, Millimeter- und Submillimeter-Astronomie, Max-Planck-Institut für Radioastronomie, Bonn, NRW, Germany; ROBIN T. GARROD, Departments of Chemistry and Astronomy, The University of Virginia, Charlottesville, VA, USA.
a
A. Belloche et al., A&A 559 (2013) Art. No. A47.
A. Belloche et al., Science 345 (2014) 1584.
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Sagittarius (Sgr for short) B2 is the most massive and luminous star-forming region in our Galaxy, located close to the
Galactic Center. We have carried out a molecular line survey with the IRAM 30 m telescope toward its two major sites
of star-formation, Sgr B2(M) and (N).a Toward the latter source, which is particularly rich in Complex Organic Molecules
(COMs), we detected three molecules for the first time in space, aminoacetonitrile, ethyl formate, and n-propyl cyanide.
We have recently obtained ALMA data of Sgr B2(N) between ∼84 and ∼111 GHz within Cycle 0 and one additional
setup up to 114.4 GHz within Cycle 1. At angular resolutions of 1.8′′ and 1.4′′ , respectively, the two main hot cores,
the prolific Sgr B2(N-LMH) (or Sgr B2(N)-SMA1) and the likely less evolved Sgr B2(N)-SMA2 are well separated, and
line confusion is reduced greatly for the latter. As a consequence, we have been able to identify the first branched alkyl
molecule in space, iso-propyl cyanide, toward Sgr B2(N)-SMA2.b Our ongoing analyses include investigations of cyanides
and isocyanides, alkanols and thioalkanols, and deuterated molecules among others. We will present some of our results.
RI06
FIRST SPECTROSCOPIC STUDIES AND DETECTION IN SgrB2 OF
2:55 – 3:10
13
C-DOUBLY SUBSTITUED ETHYL CYANIDE
L. MARGULÈS, R. A. MOTIYENKO, Laboratoire PhLAM, UMR 8523 CNRS - Université Lille 1, Villeneuve
d’Ascq, France; J.-C. GUILLEMIN, Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS - Université de Rennes 1, Rennes, France; HOLGER S. P. MÜLLER, I. Physikalisches Institut, Universität zu Köln,
Köln, Germany; ARNAUD BELLOCHE, Millimeter- und Submillimeter-Astronomie, Max-Planck-Institut für
Radioastronomie, Bonn, NRW, Germany.
Ethyl cyanide (CH3 CH2 CN) is one of the most abundant complex organic molecules in the interstellar medium firstly
detected in OMC-1 and Sgr B2 in 1977a . The vibrationally excited states are enough populated under ISM conditions
and could be detectedb ,c . Apart from the deuterated ones, all mono-substituted isotopologues of ethyl cyanide (13 Cd and
15 e
N ) have been detected in the ISM. The detection of isotopologues in the ISM is important: it can give information about
the formation process of complex organic molecules, and it is essential to clean the ISM spectra from the lines of known
molecules in order to detect new ones. The 12 C/13 C ratio found in SgrB2: 20-30 suggests that the doubly 13 C could be
present in the spectral line survey recently obtained with ALMA (EMoCA)f , but no spectroscopic studies exist up to now.
We measured and analyzed the spectra of the 13 C-doubly-substitued species up to 1 THz with the Lille solid-state based
spectrometer. The spectroscopic results and and the detection of the doubly 13 C species in SgrB2 will be presented.
This work was supported by the CNES and the Action sur Projets de l’INSU, PCMI. This work was also done under ANR-13BS05-0008-02 IMOLABS. Support by the Deutsche Forschungsgemeinschaft via SFB 956, project B3 is acknowledged
a
D. R. Johnson, et al., Astrophys. J. 1977, 218, L370
A. Belloche, et al., A&A 2013, 559, A47
c
A.M. Daly, et al., Astrophys. J. 2013, 768, 81
d
K. Demyk, et al. A&A 2007 466, 255
e
Margulès, et al. A&A 2009, 493, 565
f
Belloche et al. 2014, Science, 345, 1584
b
205
RI07
3:12 – 3:27
MILLIMETERWAVE SPECTROSCOPY OF ETHANIMINE AND PROPANIMINE AND THEIR SEARCH IN ORION
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L. MARGULÈS, R. A. MOTIYENKO, Laboratoire PhLAM, UMR 8523 CNRS - Université Lille 1, Villeneuve
d’Ascq, France; J.-C. GUILLEMIN, Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS - Université de
Rennes 1, Rennes, France; JOSE CERNICHARO, Departamento de Astrofı́sica, Centro de Astrobiologı́a CAB,
CSIC-INTA, Madrid, Spain.
a
Godfrey, P. D.; et al. Astrophys. Lett. 13, (1973) 119
Loomis, R. A.; et al. ApJ. Lett. 765, (2013) L9
c
Lovas, F. J.; et al. J. Chem. Phys. 72, (1980) 4964
d
Ilyushin, V.V. et al;J. Mol. Spectrosc. 259, (2010) 26
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The aldimines are important to understand amino acids formation process as they appear in reaction scheme of Streckertype synthesis. Following the detection in the ISM of methanimine (CH2 NH) in 1973a and the more recent one of ethanimine
(CH3 CHNH)b , we decided to investigate the next molecule in the series: propanimine (CH3 CH2 CHNH). For this molecule
no spectroscopic information was available up to now. We measured the rotational spectrum of propanimine in the frequency
range up to 500 GHz. Since the spectroscopic studies of ethanimine were limited to 130 GHzc , we also extended the measurements up to 300 GHz. The spectra of both E- and Z- isomers are analyzed for the two molecules. Usually aldimines,
which are unstable molecules, are obtained by discharge or pyrolysis methods, here pure sample were obtained by synthesis
process.
For ethanimine, the methyl top internal rotation should be taken into account, therefore the analysis is performed using new
version of RAM36 coded which includes the treatment of the nuclear quadrupole hyperfine structure.
The spectroscopic results and their searches in Orion will be presented.
This work was supported by the CNES and the Action sur Projets de l’INSU, PCMI. This work was also done under ANR-13BS05-0008-02 IMOLABS
Intermission
RI08
FURTHER STUDIES OF λ 5797.1 DIFFUSE INTERSTELLAR BAND
3:46 – 4:01
TAKESHI OKA, L. M. HOBBS, DANIEL E. WELTY, DONALD G. YORK, Department of Astronomy and
Astrophysics, The University of Chicago, Chicago, IL, USA; JULIE DAHLSTROM, Department of Physics and
Astronomy, Carthage College, Kenosha, WI, USA; ADOLF N. WITT, Department of Physics and Astronomy,
University of Toledo, Toledo, OH, USA.
The λ 5797.1 DIB is unique with its sharp central feature.a We simulated the spectrum based on three premises: (1) Its
carrier molecule is polar as concluded from the anomalous spectrum toward the star Herschel 36.b (2) The central feature is
Q-branch of a parallel band of a prolate top. (3) The radiative temperature of the environment is Tr = 2.73 K. A comparison
with observed spectrum indicated that the carrier contains 5-7 heavy atoms.c
To further strengthen this hypothesis, we have looked for vibronic satellites of the λ 5797.1 DIB. Since its anomaly
toward Her 36 was ascribed to the lengthening of bonds upon the electronic excitation, vibronic satellites involving stretch
vibrations are expected. Among the 73 DIBs observed toward HD 183143 to the blue of 5797.1 Å, two DIBs, λ 5545.1 and
λ 5494.2 stand out as highly correlated with λ 5797.1 DIB. Their correlation coefficients 0.941 and 0.943, respectively, are
not sufficiently high to establish the vibronic relation by themselves but can be explained as due to high uncertainties due
to their weakness and their stellar blends. They are above the λ 5797.1 DIB by 784.0 cm−1 and 951.2 cm−1 , respectively,
approximately expected for stretching vibrations.
Another observations which may possibly be explained by our hypothesis is the emission at 5800 Å from the Red
Rectangle Nebula called RR 5800.d Our analysis suggests that λ 5797.1 DIB and RR 5800 are consistently explained as
caused by the same molecule.
a
T.H. Kerr, R.E. Hibbins, S.J. Fossey, J.R. Miles, P.J. Sarre, ApJ 495, 941 (1998)
T. Oka, D.E. Welty, S. Johnson, D.G. York, J. Dahlstrom, L.M. Hobbs, ApJ 773, 42 (2013)
c
J. Huang, T. Oka, Mol. Phys. J.P. Maier Special Issue in press.
d
G.D. Schmidt, A.N. Witt, ApJ 383, 698 (1991)
b
206
RI09
4:03 – 4:18
LABORATORY OPTICAL SPECTROSCOPY OF THE PHENOXY RADICAL AS A DIFFUSE INTERSTELLAR BANDS
CANDIDATE
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MITSUNORI ARAKI, YUKI MATSUSHITA, Faculty of Science Division I, Tokyo University of Science,
Shinjuku-ku, Tokyo, Japan; KOICHI TSUKIYAMA, Faculty of Science Division I, Tokyo University of Science,
Shinjuku-ku, Tokyo, Japan.
a
MF14
Araki, Niwayama, and Tsukiyama, AstronomicalJournal, 148, 87 (5pp), 2014
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b
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Diffuse Interstellar Bands (DIBs) are optical absorption lines observed in diffuse clouds in interstellar space. They still
remain the longest standing unsolved problem in spectroscopy and astrochemistry, although several hundreds of DIBs have
been already detected. Aromatic radicals in a gas phase are potential DIB candidate molecules. The electronic transitions
of aromatic radicals result in optical absorption. Last year we reported the gas-phase optical absorption spectrum of the
2
A2 ← X 2 B1 transition of the thiophenoxy radical C6 H5 S using a cavity ringdown spectrometer.a,b As the next step,
we observed the B 2 A2 ← X 2 B1 transition of the phenoxy radical C6 H5 O in the discharge of anisole. The four broad and
asymmetric peaks making a progression of 500 cm−1 were detected in the 5700–6450 Åregion. The progression was assigned
to the 6a mode, and the broad and asymmetric peak profiles were accounted for by the sequences of the 10b mode. Each
vibrational component has a broad structure of 23 Å, which can be explained by lifetime broadening. Based on the assignment
of the progression and the sequences, the vibronic components from v = 0 in the X 2 B1 ground state can be extracted from the
broad and asymmetric peak profiles to compare the laboratory bands with DIBs. Although the components did not agree with
the reported DIBs, the upper limit of the column density for the phenoxy radical in the diffuse clouds toward HD 204827 was
evaluated to be 4 × 1014 cm−2 . Therefore the most fundamental aromatic radicals, the thiophenoxy and phenoxy radicals,
could not explain DIBs observed at present.
RI10
4:20 – 4:35
INVESTIGATION OF CARBONACEOUS INTERSTELLAR DUST ANALOGUES BY INFRARED SPECTROSCOPY:
EFFECTS OF ENERGETIC PROCESSING
BELÉN MATÉ, MIGUEL JIMÉNEZ-REDONDO, ISABEL TANARRO, VICTOR JOSE HERRERO, Molecular Physics, Instituto de Estructura de la Materia (IEM-CSIC), Madrid, Spain.
Carbonaceous compounds, both solids and gas-phase molecules, are found in very diverse astronomical mediaa . A significant amount of the elemental carbon is found in small dust grains. This carbonaceous dust, mostly formed in the last stages of
evolution of C-rich stars, is the carrier of characteristic IR absorption bands revealing the presence of aliphatic, aromatic and
olefinic functional groups in variable proportionsb . Among the various candidate materials investigated as possible carriers
of these bands, hydrogenated amorphous carbon (a-C:H) has led to the best agreement with the observations. Carbonaceous
grains are processed by H atoms, UV radiation, cosmic rays and interstellar shocks in their passage from asymptotic giant
branch stars to planetary nebulae and to the diffuse interstellar medium. The mechanisms of a-C:H production and evolution
in astronomical media are presently a subject of intensive investigation. In this work we present a study of the stability of
carbonaceous dust analogues generated in He+CH4 radiofrequency discharges. In order to simulate the processing of dust in
the interstellar environments, the samples have been subjected to electron bombardment, UV irradiation, and both He and H2
plasma processing. IR spectroscopy is employed to monitor the changes in the structure and composition of the carbonaceous
films.
a
b
A.G.G.M. Tielens. Rev. Mod. Phys., 85, 1021 (2013)
J.E. Chiar, A.G.G.M. Tielens, A.J. Adamson and A. Ricca. Astrophys. J., 770, 78 (2013)
207
RI11
4:37 – 4:52
4
REACTIONS OF GROUND STATE NITROGEN ATOMS N( S) WITH ASTROCHEMICALLY-RELEVANT
MOLECULES ON INTERSTELLAR DUSTS
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LAHOUARI KRIM, SENDRES NOURRY, Department of Chemistry, MONARIS, CNRS, UMR 8233, Sorbonne
Universités, UPMC Univ Paris 06, Paris, France.
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In the last few years, ambitious programs were launched to probe the interstellar medium always more accurately. One
of the major challenges of these missions remains the detection of prebiotic compounds and the understanding of reaction
pathways leading to their formation. These complex heterogeneous reactions mainly occur on icy dust grains, and their
studies require the coupling of laboratory experiments mimicking the extreme conditions of extreme cold and dilute media.
For that purpose, we have developed an original experimental approach that combine the study of heterogeneous reactions (by
exposing neutral molecules adsorbed on ice to non-energetic radicals H, OH, N...) and a neon matrix isolation study at very
low temperatures, which is of paramount importance to isolate and characterize highly reactive reaction intermediates. Such
experimental approach has already provided answers to many questions raised about some astrochemically-relevant reactions
occurring in the ground state on the surface of dust grain ices in dense molecular clouds. The aim of this new present work is
to show the implication of ground state atomic nitrogen on hydrogen atom abstraction reactions from some astrochemicallyrelevant species, at very low temperatures (3K-20K), without providing any external energy. Under cryogenic temperatures
and with high barrier heights, such reactions involving N(4 S) nitrogen atoms should not occur spontaneously and require an
initiating energy. However, the detection of some radicals species as byproducts, in our solid samples left in the dark for hours
at 10K, proves that hydrogen abstraction reactions involving ground state N(4 S) nitrogen atoms may occur in solid phase at
cryogenic temperatures. Our results show the efficiency of radical species formation stemming from non-energetic N-atoms
and astrochemically-relevant molecules. We will then discuss how such reactions, involving nitrogen atoms in their ground
states, might be the first key step towards complex organic molecules production in the interstellar medium.
RI12
4:54 – 5:09
STABILITY OF GLYCINE TO ENERGETIC PROCESSING UNDER ASTROPHYSICAL CONDITIONS INVESTIGATED VIA INFRARED SPECTROSCOPY
BELÉN MATÉ, VICTOR JOSE HERRERO, ISABEL TANARRO, RAFAEL ESCRIBANO, Molecular Physics,
Instituto de Estructura de la Materia (IEM-CSIC), Madrid, Spain.
Glycine, the simplest aminoacid, has been detected in comets and meteorites in our Solar System. Its detection in
the interstellar medium is not improbable since other organic molecules of comparable complexity have been observeda .
Information of how complex organic molecules resist the energetic processing that they may suffer in different regions of
space is of great interest for astrochemists and astrobiologists.
Further to previous investigationsb we have studied in this work, via infrared spectroscopy, the effect of 2 keV electron
bombardment on amorphous and crystalline glycine layers at low temperatures, to determine its destruction cross section
under astrophysical conditions. Energetic electrons are known to be present in the solar wind and in planetary magnetospheres,
and are also formed in the interaction of cosmic rays with matter. Moreover, we have probed the shielding effect of water
ice layers grown on top of the glycine samples at 90 K. These experiment aim to mimic the conditions of the aminoacid in
ice mantles on dust grains in the interstellar medium or in some outer Solar System objects, with a water ice surface crust.
A residual material, product of glycine decomposition, was found at the end of the processing. A tentative assignment of the
infrared spectra of the residue will be discussed in the presentation.
a
E. Herbst and E. F. van Dishoeck, Annu. Rev. Astro. Astrophys. 2009, 47:427-480
B. Maté, Y. Rodriguez-Lazcano, O. Gálvez, I. Tanarro and R. Escribano, Phys Chem Chem Phys, 2011, 13, 12268. B. Maté, I. Tanarro, M.A. Moreno, M. Jiménez-Redondo,
R. Escribano, and V. J. Herrero, Faraday Discussions, 2014, DOI: 10.1039/c3fd00132f.
b
208
RI13
MILLIMETER AND SUBMILLIMETER STUDIES OF INTERSTELLAR ICE ANALOGUES
5:11 – 5:21
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AJ MESKO, IAN C WAGNER, HOUSTON HARTWELL SMITH, Department of Chemistry, Emory University,
Atlanta, GA, USA; STEFANIE N MILAM, Astrochemistry, NASA Goddard Space Flight Center, Greenbelt, MD,
USA; SUSANNA L. WIDICUS WEAVER, Department of Chemistry, Emory University, Atlanta, GA, USA.
The chemistry of interstellar ice analogues has been a topic of great interest to astrochemists over the last 20 years.
Currently, the models of interstellar chemistry feature icy-grain reactions as a primary mechanism for the formation of many
astrochemical species as well as potentially astrobiologically-relevant complex organic molecules. This talk presents new
spectral results collected by a millimeter and submillimeter spectrometer coupled to a vacuum chamber designed to study
the sublimation or sputtered products of icy-grain reactions initiated by thermal-processing or photo-processing of interstellar
ice analogues. Initial results from thermal desorption and UV photoprocessing experiments of pure water ice and water +
methanol ice mixtures will be presented.
in
RI14
5:23 – 5:38
UNTANGLING MOLECULAR SIGNALS OF ASTROCHEMICAL ICES IN THE THz: DISTINGUISHING AMORPHOUS, CRYSTALLINE, AND INTRAMOLECULAR MODES WITH BROADBAND THz SPECTROSCOPY
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BRETT A. McGUIRE, NAASC, National Radio Astronomy Observatory, Charlottesville, VA, USA; SERGIO
IOPPOLO, Department of Physical Sciences, The Open University, Milton Keynes, UK; XANDER DE VRIES,
Theoretical Chemistry, University of Nijmegen, Nijmegen, Netherlands; MARCO A. ALLODI, BRANDON
CARROLL, GEOFFREY BLAKE, Division of Chemistry and Chemical Engineering, California Institute of
Technology, Pasadena, CA, USA.
We have previous reported at this meeting on the initial construction of a broadband (0.3 – 7.5 THz) TeraHertz timedomain spectrometer to study condensed-phase samples of astrophysically-relevant species. Here, we present the latest
results from this instrument, focusing on the intersection of theory with experiment in the interpretation of our spectra. We will
present both simple (CO2 ) and more complex (CH3 OH and beyond) species, in their purely-crystalline and purely-amorphous
states, at varying levels of matrix isolation, and as mixtures of these species. We will discuss the relative contributions of
individual molecular motions (i.e. torsional modes) and bulk motions within the ice to the observed laboratory spectra. We
will also touch upon the feasibility of direct interstellar detection of species from these spectra, and the results of proof-ofconcept observations with the FIFI-LS instrument on the SOFIA telescope, currently scheduled for Spring 2015.
RI15
5:40 – 5:55
+
QUANTUM CHEMICAL STUDY OF THE REACTION OF C WITH INTERSTELLAR ICE: PREDICTIONS OF VIBRATIONAL AND ELECTRONIC SPECTRA OF REACTION PRODUCTS
DAVID E. WOON, Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL, USA.
The C+ cation (CII) is the dominant form of carbon in diffuse clouds and an important tracer for star formation in
molecular clouds. We studied the low energy deposition of C+ on ice using density functional theory calculations on water
clusters as large as 18 H2 O. Barrierless reactions occur with water to form two dominant sets of products: HOC + H3 O+ and
CO− + 2H3 O+ . In order to provide testable predictions, we have computed both vibrational and electronic spectra for pure
ice and processed ice clusters. While vibrational spectroscopy is expected to be able to discern that C+ has reacted with ice
by the addition of H3 O+ features not present in pure ice, it does not provided characteristic bands that would discern between
HOC and CO− . On the other hand, predictions of electronic spectra suggest that low energy absorptions may occur for CO−
and not HOC, making it possible to distinguish one product from the other.
209
RJ. Cold/Ultracold/Matrices/Droplets
RJ01
IR SPECTRA OF COLD PROTONATED METHANE
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Chair: Gary E. Douberly, The University of Georgia, Athens, GA, USA
1:30 – 1:45
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OSKAR ASVANY, I. Physikalisches Institut, Universität zu Köln, Köln, Germany; KOICHI MT YAMADA,
EMTech, National Institute of Advanced Industrial Science and Technology (AIST) , Tsukuba, Japan; SANDRA
BRÜNKEN, ALEXEY POTAPOV, STEPHAN SCHLEMMER, I. Physikalisches Institut, Universität zu Köln,
Köln, Germany.
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High-resolution infrared spectra of mass selected protonated methane, CH+
5 , have been recorded in the C-H stretching
region in a 22-pole ion trap experiment at low temperatures. The frequencies of the infrared OPO system (pump and signal)
have been calibrated using a NIR frequency comb. As a result the ro-vibrational IR transition frequencies of CH+
5 could be
determined to an accuracy in the MHz regime.a In this contribution we discuss different techniques of laser induced reactions
which enabled recording spectra at different temperatures.b The spectra simplify dramatically at a nominal trap temperature
of 4 K. Nevertheless an assignment of these spectra is very difficult. We apply the idea of the Rydberg-Ritz combination
principle to the complex spectra of protonated methane in order to get first hints at the energy level structure of this enigmatic
molecule.
a
O. Asvany, J. Krieg, and S. Schlemmer, Frequency comb assisted mid-infrared spectroscopy of cold molecular ions, Review of Scientific Instruments, 83 (2012), 076102.
O. Asvany, S. Brünken, L. Kluge, and S. Schlemmer, COLTRAP: a 22-pole ion trapping machine for spectroscopy at 4 K, Applied Physics B: Lasers and Optics, 114 (2014),
203-211
b
RJ02
PROGRESS ON OPTICAL ROTATIONAL COOLING OF SiO+
1:47 – 2:02
PATRICK R STOLLENWERK, YEN-WEI LIN, BRIAN C. ODOM, Department of Physics and Astronomy,
Northwestern University, Evanston, IL, USA.
Producing ultracold molecules is the first step in precision molecular spectroscopy. Here we present some of the challenges and advantages of SiO+ as well as some of our progress toward meeting those challenges. To demonstrate ground state
SiO+, we first load about 100 SiO+ via 2+1 REMPI into an ion trap. Translational motion of SiO+ is then sympathetically
cooled by co-trapped Ba+, which is laser cooled. To prepare the population into the ground state, we optically pump the
P-branch (rotational cooling transitions) in the B:Σ(v’=0) ← X:Σ(v=0) band with broadband radiation. Because the band
is highly diagonal, population can be effectively driven into the rotational ground state before falling into other manifolds.
The broadband source, a fs laser, is spectrally filtered using an ultrashort pulse shaping technique to drive only the P-branch.
Attention must be paid when aligning the optics to obtain sufficient masking resolution. We have achieved 3 cm−1 resolution,
which is sufficient to modify a broadband source for rotationally cooling SiO+.
210
RJ03
THE OPTICAL BICHROMATIC FORCE IN MOLECULAR SYSTEMSa
2:04 – 2:19
LELAND M. ALDRIDGE, SCOTT E. GALICA, EDWARD E. EYLER, Department of Physics, University of
Connecticut, Storrs, CT, USA.
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The bichromatic optical force (BCF), which can greatly exceed radiative forces, seems ideal for laser slowing and cooling
of molecules because it minimizes the effects of radiative decay. However, it relies on sustained coherences between optically
coupled states, and molecules, with their many sublevels and decay pathways, present new challenges in maintaining these
coherences compared with simple atoms. We have conducted extensive numerical simulations of BCFs in model molecular
systems based on the B ↔ X transition in CaF, and have begun experimental tests in a molecular beam.
Supported by the National Science Foundation
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In our modeling, the effects of fine and hyperfine structure are examined using a simplified level scheme that is still
sufficiently complete to include the major pathways leading to loss or decoherence. To circumvent optical pumping into
coherent dark states we explore two possible schemes: (1) a skewed dc magnetic field, and (2) rapid optical polarization
switching. The effects of repumping to compensate for out-of-system radiative decay are also examined. Our results verify
that the BCF is a promising method for creating large forces in molecular beams while minimizing out-of-system radiative
losses, and provide detailed guidance for experimental designs. Compared to a two-level atom, the peak force is reduced
by about an order of magnitude, but there is little reduction in the velocity range over which the force is effective. Our
experiments on deflection and slowing using the CaF B ↔ X, (0-0) transition, still at an early stage, include studies of
both the P11 (1.5)/P Q12 (0.5) branch, a quasi-cycling configuration with extensive hfs, and the R11 (0.5)/R Q21 (0.5) branch,
which has a much simpler hfs but requires rotational repumping.
RJ04
A NEW EQUATION OF STATE FOR SOLID para-HYDROGEN
2:21 – 2:36
LECHENG WANG, ROBERT J. LE ROY, PIERRE-NICHOLAS ROY, Centre for Graduate Work in Chemistry
and Biochemistry, University of Waterloo, Waterloo, Ontario, Canada.
Solid para-H2 is a popular accommodating host for impurity spectroscopy due to its unique softness and the spherical
symmetry of para-H2 in its J=0 rotational level.a,b To simulate the properties of impurity-doped solid para-H2 , a reliable
model for the ‘soft’ pure solid para-H2 at different pressures is highly desirable. While a couple of experimentalc and
theoreticald studies aimed at elucidating the equation of state (EOS) of solid para-H2 have been reported, the calculated
EOS was shown to be heavily dependent on the potential energy surface (PES) between two para-H2 that was used in the
simulations.e The current study also demonstrates that different choices of the parameters governing the Quantum Monte
Carlo simulation could produce different EOS curves.
To obtain a reliable model for pure solid para-H2 , we used a new 1-D para-H2 PES reported by Faruk et al.f that was
obtained by averaging over Hinde’s highly accurate 6-D H2 –H2 PES.g The EOS of pure solid para-H2 was calculated using
the PIMC algorithm with periodic boundary conditions (PBC). To precisely determine the equilibrium density of solid paraH2 , both the value of the PIMC time step τ and the number of particles in the PBC cell were extrapolated to convergence.
The resulting EOS agreed well with experimental observations, and the hcp structured solid para-H2 was found to be more
stable than the fcc one at 4.2K, in agreement with experiment. The vibrational frequency shift of para-H2 as a function of the
density of the pure solid was also calculated, and the value of the shift at the equilibrium density is found to agree well with
experiment.
a
T. Momose, H. Honshina, M. Fushitani and H. Katsuki, Vib. Spectrosc. 34, 95(2004).
M. E. Fajardo, J. Phys. Chem. A 117, 13504 (2013).
c
I. F. Silvera, Rev. Mod. Phys. 52, 393(1980).
d
F. Operetto and F. Pederiva, Rhys. Rev. B 73, 184124(2006).
e
T. Omiyinka and M. Boninsegni, Rhys. Rev. B 88, 024112(2013).
f
N. Faruk, M. Schmidt, H. Li, R. J. Le Roy, and P.-N. Roy,J. Chem. Phys. bf 141, 014310(2014).
g
R. J. Hinde, J. Chem. Phys. 128, 154308(2008).
b
211
RJ05
INFRARED SPECTROSCOPY OF NOH SUSPENDED IN SOLID PARAHYDROGEN: PART TWO
2:38 – 2:53
MORGAN E. BALABANOFF, FREDRICK M. MUTUNGA, DAVID T. ANDERSON, Department of Chemistry, University of Wyoming, Laramie, WY, USA.
a
b
G. Maier, H. P. Reisenauer, M. De Marco, Angew. Chem. Int. Ed. 38, 108-110 (1999).
U. Bozkaya, J. M. Turney, Y. Yamaguchi, and H. F. Schaefer III, J. Chem. Phys. 136, 164303 (2012).
David T. Anderson and Mahmut Ruzi, 68th Ohio State University International Symposium on Molecular Spectroscopy, talk TE01 (2013).
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The only report in the literature on the infrared spectroscopy of the parent oxynitrene NOH was performed using Ar
matrix isolation spectroscopy at 10 K.a In this previous study, they performed detailed isotopic studies to make definitive
vibrational assignments. NOH is predicted by high-level calculations to be in a triplet ground electronic state,b but the Ar
matrix isolation spectra cannot be used to verify this triplet assignment. In our 2013 preliminary report,c we showed that 193
nm in situ photolysis of NO trapped in solid parahydrogen can also be used to prepare the NOH molecule. Over the ensuing
two years we have been studying the infrared spectroscopy of this species in more detail. The spectra reveal that NOH can
undergo hindered rotation in solid parahydrogen such that we can observe both a-type and b-type rovibrational transitions
for the O-H stretch vibrational mode, but only a-type for the mode assigned to the bend. In addition, both observed a-type
infrared absorption features (bend and OH stretch) display fine structure; an intense central peak with weaker peaks spaced
symmetrically to both lower and higher wavenumbers. The spacing between the peaks is nearly identical for both vibrational
modes. We now believe this fine structure is due to spin-rotation interactions and we will present a detailed analysis of
this fine structure. Currently, we are performing additional experiments aimed at making 15 NOH to test these preliminary
assignments. The most recent data and up-to-date analysis will be presented in this talk.
RJ06
HIGH RESOLUTION INFRARED SPECTROSCOPY OF CH3 F-(ortho-H2 )n CLUSTER IN SOLID para-H2
2:55 – 3:10
HIROYUKI KAWASAKI, ASAO MIZOGUCHI, HIDETO KANAMORI, Department of Physics, Tokyo Institute
of Technology, Tokyo, Japan.
The absorption spectrum of the ν 3 (C-F stretching) mode of CH3 F in solid para-H2 by FTIR showed a series of equal
interval peaksa . Their interpretation was that the n-th peak of this series was due to CH3 F-(ortho-H2 )n clusters which were
formed CH3 F and n’s ortho-H2 in first nearest neighbor sites of the para-H2 crystal with hcp structure. In order to understand
this system in more detail, we have studied these peaks, especially n = 0 – 3 corresponding to 1037 - 1041 cm−1 , by using
high-resolution and high-sensitive infrared quantum cascade (QC) laser spectroscopy. Before now, we found many peaks
around each n-th peak of the cluster, which we didn’t know their originsb . We observed photochromic phenomenon of these
peaks by taking an advantage of the high brightness of the laserc . In this study, we focus on satellite series consisting of
six peaks which locate at the lower energy side of each main peak. All the peaks showed a common red shouldered line
profile, which corresponds to partly resolved transitions of ortho- and para- CH3 F. The spectral pattern and time behavior
of the peaks may suggest that these satellite series originate from a family of CH3 F clusters involving ortho-H2 in second
nearest neighbor sites. A model function assuming this idea is used to resolve the observed spectrum into each Lorentzian
component, and then some common features of the satellite peaks are extracted and the physical meanings of them will be
discussed.
a
K. Yoshioka and D. T. Anderson, J. Chem. Phys. 119 (2003) 4731-4742
A. R. W. McKellar, A. Mizoguchi, and H. Kanamori, J. Chem. Phys. 135 (2011) 124511
c
A. R. W. McKellar, A. Mizoguchi, and H. Kanamori, Phys. Chem. Chem. Phys. 13 (2011) 11587-11589
b
Intermission
212
RJ07
3:29 – 3:44
4
REACTIVE INTERMEDIATES IN He NANODROPLETS: INFRARED LASER STARK SPECTROSCOPY OF DIHYDROXYCARBENE
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BERNADETTE M. BRODERICK, CHRISTOPHER P. MORADI, GARY E. DOUBERLY, Department of
Chemistry, University of Georgia, Athens, GA, USA; LAURA McCASLIN, JOHN F. STANTON, Department
of Chemistry, The University of Texas, Austin, TX, USA.
in
Singlet dihydroxycarbene (HOCOH) is produced via pyrolytic decomposition of oxalic acid, captured by helium nanodroplets, and probed with infrared laser Stark spectroscopy. Rovibrational bands in the OH stretch region are assigned to
either trans,trans- or trans,cis- rotamers on the basis of symmetry type, nuclear spin statistical weights, and comparisons to
electronic structure theory calculations. Stark spectroscopy provides the inertial components of the permanent electric dipole
moments for these rotamers. The dipole components for trans,trans- and trans,cis- rotamers are (µa , µb ) = (0.00, 0.68(6))
and (1.63(3), 1.50(5)), respectively. The infrared spectra lack evidence for the higher energy cis,cis- rotamer, which is consistent with a previously proposed pyrolytic decomposition mechanism of oxalic acid and computations of HOCOH torsional
interconversion and tautomerization barriers.
RJ08
3:46 – 4:01
INFRARED LASER STARK SPECTROSCOPY OF THE PRE-REACTIVE Cl···HCl COMPLEX FORMED IN SUPERFLUID 4 He DROPLETS
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CHRISTOPHER P. MORADI, GARY E. DOUBERLY, Department of Chemistry, University of Georgia, Athens,
GA, USA.
Chlorine atoms, generated through the thermal decomposition of Cl2 , are solvated in superfluid helium nanodroplets and
clustered with HCl molecules. The H–Cl stretching modes of these clusters are probed via infrared laser spectroscopy. A
broad band centered at ≈2880.9 cm−1 is assigned to the binary Cl···HCl complex. The band center is red shifted by only
7.4 cm−1 from the “free” HCl stretch (ν1 ) of (HCl)2 and, as such, is consistent with an assignment to a similarly “free” HCl
stretch. Also, the breadth of the band (≈2 cm−1 FWHM) is consistent with assignment to a mostly b-type component of
the H–Cl stretch; the band is lifetime broadened to a similar extent as the predominantly b-type ν1 stretch of (HCl)2 , due
to fast rotational relaxation facilitated by the helium droplet environment. Despite the lack of rotational structure, which
would verify our assignment, the spectrum is consistent with stabilization of a weakly-bound complex having an L-shaped
geometry. Computations reveal that the projection of the transition dipole moment onto the a-axis results in a dramatic
decrease (≈700 times) in the intensity of the a-type band relative to the b-type band intensity; indeed, the signal-to-noise ratio
in our experiment precluded observation of an a-type band for this complex. No bands were observed that could derive from
a strongly H-bonded Cl···HCl complex. Additionally, we located two bands at 2764.0 and 2798.5 cm−1 that are consistent
with the pick-up of two HCl molecules and are therefore assigned to vibrations of the Cl···(HCl)2 complex.
RJ09
HELIUM NANODROPLET INFRARED SPECTROSCOPY OF THE TROPYL RADICAL
4:03 – 4:13
MATIN KAUFMANN, Physikalische Chemie II, Ruhr University Bochum, Bochum, Germany; BERNADETTE
M. BRODERICK, GARY E. DOUBERLY, Department of Chemistry, University of Georgia, Athens, GA, USA.
Helium nanodroplet spectroscopy is a well-established experimental technique to study weakly bound complexes and reactive species. The superfluid helium interacts weakly with the embedded species, leading to only small matrix-induced shifts
in vibrational spectra. This technique has been applied for the spectroscopic study of the resonance-stabilized allyl radical
and its reactions and complexes.a,b The tropyl radical is another example of a π-conjugated radical, being of importance as a
reaction intermediate in organic chemistry. Having an electron in a pair of degenerate orbitals, its geometry is subject to the
Jahn-Teller effect.c The Jahn-Teller distortion of the ground electronic state is probed with IR laser spectroscopy.
a
C. M. Leavitt, C. P. Moradi, B. W. Acrey, G. E. Douberly; J. Chem. Phys. 2013, 139, 234301.
D. Leicht, D. Habig, G. Schwaab, M. Havenith; J. Phys. Chem. A 2015, 119, 1007.
c
E. P. F. Lee, T. G. Wright; J. Phys. Chem. A 1998, 102, 4007.
b
213
RJ10
MICROSOLVATION STUDIES IN HELIUM NANODROPLETS
4:15 – 4:30
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GERHARD SCHWAAB, MATIN KAUFMANN, DANIEL LEICHT, RAFFAEL SCHWAN, THEO FISCHER,
DEVENDRA MANI, MARTINA HAVENITH, Physikalische Chemie II, Ruhr University Bochum, Bochum,
Germany.
In bulk aqueous solutions the interactions between solute and solvent are still not fully understood. We apply spectroscopy in Helium nanodroplets to investigate solvation processes step by step (bottom up approach). Recently, the Bochum
helium nanodroplet spectrometer has been equipped with a quantum cascade laser spanning the frequency ranges from 1000–
1400, 1600–1700, and 2500–2600 cm−1 . First results with the extended setup will be presented.
RJ11
4:32 – 4:47
INFRARED SPECTRA OF THE CO2 -H2 O, CO2 -(H2 O)2 , and (CO2 )2 -H2 O COMPLEXES ISOLATED IN SOLID NEON
BETWEEN 90 AND 5300 cm−1
in
BENOÎT TREMBLAY, Chemistry/ MONARIS, CNRS, UMR 8233, Sorbonne Universités, UPMC Univ Paris 06,
Paris, France; PASCALE SOULARD, MONARIS UMR8233, CNRS - UNiversité Paris 6 UPMC, Paris, France.
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The van der Waals complex of H2 O with CO2 has attracted considerable theoretical interest since it is a typical example
of a weak binding complex (less than 3 kcal/mol), but a very few IR data are available in gas. For these reasons, we have
studied in solid neon hydrogen bonded complexes involving carbon dioxide and water molecules. Evidence for the existence
of at least three (CO2 )m (H2 O)n , or m:n, complexes has been obtained from the appearance of many new absorptions near the
well-know monomers fundamental transitions. Concentration effects and detailed vibrational analysis allowed identification
of fifteen, eleven and four transitions for the 1:1, 1:2, and 2:1 complexes, respectively. Careful examination of the far
infrared allows the assignment of several 1:1 and 1:2 intermolecular modes, confirmed by the observation of combinations
of intra+intermolecular transitions. All of these results significantly increase the number of one and, especially, two quanta
vibrational transitions observed for these complexes, and anharmonic coupling constants have been derived. This study
shows the high sensibility of the solid neon isolation for the spectroscopy of the hydrogen-bonded complexes since two
quanta transitions can’t be easily observed in gas phase.
RJ12
MATRIX ISOLATION AND COMPUTATIONAL STUDY OF [2C, 2N, X] (X=S, SE) ISOMERS
4:49 – 4:59
TAMAS VOROS, GYORGY TARCZAY, Institute of Chemistry, Eotvos University, Budapest, Hungary.
The [2C, 2N, S] and the [2C, 2N, Se] systems were investigated by quantum chemical computations and matrix isolation
IR spectroscopy. For both systems nine isomers were computationally investigated, for which harmonic and anharmonic
vibrational wavenumbers and infrared (IR) intensities were calculated using the CCSD(T)/aug-cc-pVTZ level of theory. The
results show that each of the isomers have two or more detectable bands in the mid IR region, which have one or two orders
of magnitude larger intensity compared to the IR intensity of the most intense bands of the most stable NCSCN and NCSeCN
isomers’. It follows that if the most stable isomers can be detected, then the other previously unobserved isomers generated
from NCSCN or NCSeCN should also be detectable with IR spectroscopy. UV spectra were also computed for each isomer
at the TD-DFT B3LYP/aug-cc-pVTZ level of theory. These computations showed that the most stable isomers (NCSCN and
NCSeCN) can absorb the UV radiation around 250 nm, and the irradiation may promote photoisomerization. This means that
if the initial isomers are irradiated by narrow-band UV radiation, new isomers may be generated, which likely decompose by
irradiating broad-band UV radiation.
The two most stable isomers, sulphur dicyanide (NCSCN) and selenium dicyanide (NCSeCN), were prepared following
literature methods. The matrix isolation IR spectra of these molecules in Ar and Kr were measured for the first time. As
a result of a selective 254 nm-irradiation of the deposited matrices some new bands appeared in the IR spectra, while the
intensity of the bands of NCSCN or NCSeCN were decreased at the same time. Irradiation of the matrices with broad-band
UV light decreased the intensity of the bands corresponding to the deposited isomers and some of the bands appeared on the
254 nm-irradiation. On the basis of the analysis of the formation rates of the different bands upon 254 nm photolysis and
by comparison with the results of the quantum chemical calculations these bands could be assigned to new isomers. In the
case of sulphur analogue NCSNC and NCNCS were unambiguously identified, and for selenium analogue the formation of
NCSeNC and NCNCSe isomers were observed.
214
RJ13
5:01 – 5:16
MATRIX ISOLATION SPECTROSCOPY AND PHOTOCHEMISTRY OF TRIPLET 1,3-DIMETHYLPROPYNYLIDENE
(MeC3 Me)
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STEPHANIE N. KNEZZ, Department of Chemistry, The Univeristy of Wisconsin, Madison, WI, USA; TERESE
A WALTZ, Department of Chemistry, Geoscience, and Physics, Edgewood College, Madison, WI, USA; BENJAMIN C. HAENNI, Department of Chemistry, University of Wisconsin–Madison, Madison, WI, USA; NICOLA
J. BURRMANN, Department of Chemistry, Heartland Community College, Normal, IL, USA; ROBERT J.
McMAHON, Department of Chemistry, The Univeristy of Wisconsin, Madison, WI, USA.
in
Acetylenic carbenes and conjugated carbon chain molecules of the HCn H family are relevant to the study of combustion and chemistry in the interstellar medium (ISM). Propynylidene (HC3 H) has been thoroughly studied and its structure
and photochemistry determined.a Here, we produce triplet diradical 1,3-dimethylpropynylidene (MeC3 Me) photochemically
from a precursor diazo compound in a cryogenic matrix (N2 or Ar) at 10 K, and spectroscopic analysis is carried out. The
infrared, electronic absorption, and electron paramagnetic resonance spectra were examined in light of the parent (HC3 H)
system to ascertain the effect of alkyl substituents on delocalized carbon chains of this type. Computational analysis, EPR,
and infrared analysis indicate a triplet ground state with a quasilinear structure. Infrared experiments reveal photochemical
reaction to penten-3-yne upon UV irradiation. Further experimental and computational results pertaining to the structure and
photochemistry will be presented.
a
Seburg, R. A.; Patterson, E. V.; McMahon, R. J., Structure of Triplet Propynylidene (HCCCH) as Probed by IR, UV/vis, and EPR Spectroscopy of Isotopomers. Journal of the
American Chemical Society 2009, 131 (26), 9442-9455.
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RJ14
5:18 – 5:33
EVIDENCE OF INTERNAL ROTATION IN THE O-H STRETCHING REGION OF THE 1:1 METHANOL-BENZENE
COMPLEX IN AN ARGON MATRIX
JAY AMICANGELO, IAN CAMPBELL, JOSHUA WILKINS, School of Science (Chemistry), Penn State Erie,
Erie, PA, USA.
Co-depositions of methanol (CH3 OH) and benzene (C6 H6 ) in an argon matrix at 20 K result in the formation of a 1:1
methanol-benzene complex (CH3 OH-C6 H6 ) as evidenced by the observation of distinct infrared bands attributable to the
complex near the O-H, C-H, and C-O stretching fundamental vibrations of CH3 OH and the hydrogen out-of-plane bending fundamental vibration of C6 H6 . Co-deposition experiments were also performed using isotopically labeled methanol
(CD3 OD) and benzene (C6 D6 ) and the corresponding deuterated complexes were also observed. Based on ab initio and
density functional theory calculations, the structure of the complex is thought to be an H-π complex in which the CH3 OH is
above the C6 H6 ring with the OH hydrogen atom interacting with the π cloud of the ring. Close inspection of the O-H and
O-D stretching peaks of the complexes reveals small, distinct satellite peaks that are approximately 3 – 4 cm−1 lower than
the primary peak. A series of experiments have been performed to ascertain the nature of the satellite peaks. These consist
of co-depositions in which the concentrations of both monomers were varied over a large range (1:200 to 1:1600 S/M ratios),
annealing experiments (20 K to 35 K), and lower temperature cycling experiments (20 K to 8 K). Based on the results of
these experiments, it is concluded that the satellite peaks are due to rotational structure and not due to matrix site effects,
higher aggregation or distinct complex geometries. Given the rigidity of a low temperature argon matrix, it is proposed that
the rotational motion responsible for the satellite peaks is internal rotation within the methanol subunit of the complex rather
than overall molecular rotation of the complex.
215
FA. Electronic structure, potential energy surfaces
Friday, June 26, 2015 – 8:30 AM
Chair: Timothy Steimle, Arizona State University, Tempe, AZ, USA
8:30 – 8:45
5
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FA01
5
CHARACTERIZATION OF THE 1 Πu - 1 Πg BAND OF C2 BY TWO-COLOR RESONANT FOUR-WAVE MIXING
AND LIF
PETER RADI, General Energy, Paul Scherrer Institute, Villigen, Switzerland.
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The application of two-color resonant four-wave mixing (TC-RFWM) in combination with a discharge slit-source in
a molecular beam environment is advantageous for the study of perturbations in C2 . Initial investigations have shown the
potential of the method by a detailed deperturbation of the d 3 Πg , v = 4 state.a
The deperturbation of the d 3 Πg , v = 6 state unveiled the presence of the energetically lowest high-spin state of C2 .
This dark state gains transition strength through the perturbation process with the d 3 Πg , v = 6 state yielding weak spectral
features that are observable by the high sensitivity of the TC-RFWM technique. The successful deperturbation study of the
d 3 Πg , v = 6 state resulted in the spectroscopic characterization of the quintet (1 5 Πg ) and an additional triplet state (b 3 Σ−
g ,
v = 19). b
More recently, investigations have been performed by applying unfolded TC-RFWM to obtain further information on
the quintet manifold. The first high-spin transition (1 5 Πu - 1 5 Πg ) has been observed via an intermediate “gateway” state
exhibiting both substantial triplet and quintet character owing to the perturbation between the 1 5 Πg , v = 0 and the d 3 Πg ,
v = 6 states. The high-lying quintet state is found to be predissociative and displays a shallow potential that accommodates
three vibrational levels only. c
Further studies of the high-spin system will be presented in this contribution. By applying TC-RFWM and laser-induced
fluorescence, data on the vibrational structure of the 1 5 Πu - 1 5 Πg system is obtained. The results are combined with highlevel ab initio computations at the multi-reference configuration interaction (MRCI) level of theory and the largest possible
basis currently implemented in the 2012 version of MOLPRO.
a
b
c
P. Bornhauser, G. Knopp, T. Gerber, and P.P. Radi, Journal of Molecular Spectroscopy 262, 69 (2010)
P. Bornhauser, Y. Sych, G. Knopp, T. Gerber, and P.P. Radi, Journal of Chemical Physics 134, 044302 (2011)
Bornhauser, P., Marquardt, R., Gourlaouen, C., Knopp, G., Beck, M., Gerber, T., van Bokhoven, JA, and Radi, P. P., Journal of Physical Chemistry, submitted
FA02
8:47 – 9:02
SIGN CHANGES IN THE ELECTRIC DIPOLE MOMENT OF EXCITED STATES IN RUBIDIUM-ALKALINE EARTH
DIATOMIC MOLECULES
JOHANN V. POTOTSCHNIG, Institute of Experimental Physics, Graz University of Technology, Graz, Austria;
FLORIAN LACKNER, UXSL, Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley,
CA, USA; ANDREAS W. HAUSER, WOLFGANG E. ERNST, Institute of Experimental Physics, Graz University of Technology, Graz, Austria.
In a recent series of combined experimental and theoretical studies we investigated the ground state and several excited states of the Rb-alkaline earth molecules RbSra and RbCa.b The group of alkali-alkaline earth (AK-AKE) molecules
has drawn attention for applications in ultracold molecular physics and the measurement of fundamental constantsc due to
their large permanent electric and magnetic dipole moments in the ground state. These properties should allow for an easy
manipulation of the molecules and simulations of spin models in optical lattices.d
In our studies we found that the permanent electric dipole moment points in different directions for certain electronically
excited states, and changes the sign in some cases as a function of bond length. We summarize our results, give possible
causes for the measured trends in terms of molecular orbital theory and extrapolate the tendencies to other combinations of
AK and AKE - elements.
a
F. Lackner, G. Krois, T. Buchsteiner, J. V. Pototschnig, and W. E. Ernst, Phys. Rev. Lett., 2014, 113, 153001; G. Krois, F. Lackner, J. V. Pototschnig, T. Buchsteiner, and W.
E. Ernst, Phys. Chem. Chem. Phys., 2014, 16, 22373; J. V. Pototschnig, G. Krois, F. Lackner, and W. E. Ernst, J. Chem. Phys., 2014, 141, 234309
b
J. V. Pototschnig, G. Krois, F. Lackner, and W. E. Ernst, J. Mol. Spectrosc., in Press (2015), doi:10.1016/j.jms.2015.01.006
c
M. Kajita, G. Gopakumar, M. Abe, and M. Hada, J. Mol. Spectrosc., 2014, 300, 99-107
d
A. Micheli, G. K. Brennen, and P. Zoller, Nature Physics, 2006, 2, 341-347
216
FA03
9:04 – 9:19
HIGH RESOLUTION VELOCITY MAP IMAGING PHOTOELECTRON SPECTROSCOPY OF THE BERYLLIUM OXIDE ANION, BEO-
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AMANDA REED, KYLE MASCARITOLO, MICHAEL HEAVEN, Department of Chemistry, Emory University, Atlanta, GA, USA.
in
The photodetachment spectrum of BeO− has been studied for the first time using high resolution velocity map imaging
photoelectron spectroscopy. Vibrational contours were imaged and compared with Franck-Condon simulations for the ground
and excited states of the neutral. The first measured electron affinity of BeO, and anisotropies of several transitions were also
measured. Experimental findings are compared to high level ab initio calculations.
FA04
9:21 – 9:36
ELECTRONIC AUTODETACHMENT SPECTROSCOPY AND IMAGING OF THE ALUMINUM MONOXIDE ANION,
ALO-
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AMANDA REED, KYLE MASCARITOLO, ADRIAN GARDNER, MICHAEL HEAVEN, Department of
Chemistry, Emory University, Atlanta, GA, USA.
The 1 Σ+ ←1 Σ+ ground state to dipole bound state electronic transition of AlO− has been studied with both rotationally resolved autodetachment spectroscopy and high resolution velocity map imaging photoelectron spectroscopy in a newly
′′
constructed apparatus. Vibrational and rotational molecular constants have been determined for both the ground state (ν =
′
0,1) and excited dipole bound state (ν = 0,1) of the aluminum monoxide anion. The spectra yield the electron binding energy
of the dipole bound state, and a more accurate electron affinity for AlO. The photoelectron anisotropies of several transitions
were measured. Experimental findings are compared to high level ab initio calculations. Additionally, high resolution photodetachment imaging of AlO− 1 Σ+ within energy ranges well above the detachment threshold were measured and compared
to previous, low resolution photodetachment results.
FA05
9:38 – 9:53
+
SPECTROSCOPY OF THE LOW-ENERGY STATES OF BaO
JOSHUA BARTLETT, ROBERT A. VANGUNDY, MICHAEL HEAVEN, Department of Chemistry, Emory
University, Atlanta, GA, USA.
The BaO+ cation is a promising candidate for studies conducted at ultra-cold temperatures. It is known that the ion
can be formed by the reaction of laser-cooled Ba+ with N2 O or O2 . Spectroscopic data are now needed for the BaO+
cation, for both characterization of the internal state population distributions and the design of population transfer schemes.
We have obtained the first spectroscopic data for BaO+ using the pulsed-field ionization, zero kinetic energy (PFI-ZEKE)
photoelectron technique. Two-color ionization was carried out via the A1 Σ+ -X1 Σ+ transition of BaO. Vibronic levels of
the X2 Σ+ , A2 Π3/2 and A2 Π1/2 states of BaO+ have been characterized. The results are compared with the predictions of
high-level electronic structure calculations.
Intermission
217
FA06
10:12 – 10:27
THE OPTICAL SPECTRUM OF SrOH RE-VISITED: ZEEMAN EFFECT, HIGH-RESOLUTION SPECTROSCOPY AND
FRANCK-CONDON FACTORS.
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TRUNG NGUYEN, DAMIAN L KOKKIN, TIMOTHY STEIMLEa , Department of Chemistry and Biochemistry, Arizona State University, Tempe, AZ, USA; IVAN KOZYRYEV, JOHN M. DOYLE, Department of Physics,
Harvard University, Cambridge, MA, USA.
a
in
Motivated by a diverse range of applications in physics and chemistry, currently there is great interest in the cooling
of molecules to very low temperatures (≤1 mK). Direct laser cooling has been previously demonstrated for the diatomic
radicals SrFb,c , YOd,e , and CaFf , and most recently a three-dimensional magneto-optical trap (MOT) of SrF molecules was
achievedg,h . To determine the possibility of laser cooling for polyatomic molecules containing three or more atoms, detailed
information is required about their Franck-Condon factors (FCFs) for emission from the excited states of interest. Here we
report on the high-resolution laser excitation spectra, recorded field-free and in the presence of a static magnetic field, and on
the dispersed fluorescence (DF) spectra for the A2 Π1/2 ← X 2 Σ+ and B 2 Σ+ ← X 2 Σ+ electronic transitions of SrOH. The
DF spectra were analyzed to precisely determine FCFs and compared with values predicted using a normal coordinate GF
matrix approach. The recorded Zeeman spectra were analyzed to determine the magnetic moments. Implication for proposed
laser cooling and trapping experiments for SrOH will be presented.
NSF CHE-1265885
E.S. Shuman, J.F. Barry and D. DeMille, Nature 467, 820 (2010)
J.F. Barry, E.S. Shuman, E.B. Norrgard and D. DeMille, Phys. Rev. Lett. 108, 103002 (2012)
d
M.T. Hummon, M. Yeo, B.K. Stuhl, A.L. Collopy, Y. Xia, and J. Ye, Phys. Rev. Lett. 110, 143001 (2013)
e
M. Yeo, M.T. Hummon, A.L. Collopy, B. Yan, B. Hemmerling, E. Chae, J.M. Doyle, and J. Ye, arXiv:1501.04683 (2015)
f
V. Zhelyazkova, A. Cournol, T.E. Wall, A. Matsushima, J.J. Hudson, E.A. Hinds, M.R. Tarbutt, and B.E. Sauer, Phys. Rev. A 89, 053416 (2014)
g
J.F. Barry, D.J. McCarron, E.B. Norrgard, M.H. Steinecker and D. DeMille, Nature 512, 286 (2014)
h
D.J. McCarron, E.B. Norrgard, M.H. Steinecker and D. DeMille, arXiv:1412.8220 (2014)
b
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c
FA07
SPECTROSCOPIC ACCURACY IN QUANTUM CHEMISTRY: A BENCHMARK STUDY ON Na3
10:29 – 10:44
ANDREAS W. HAUSER, JOHANN V. POTOTSCHNIG, WOLFGANG E. ERNST, Institute of Experimental
Physics, Graz University of Technology, Graz, Austria.
Modern techniques of quantum chemistry allow the prediction of molecular properties to good accuracy, provided the
systems are small and their electronic structure is not too complex. For most users of common program packages, ‘chemical’
accuracy in the order of a few kJ/mol for relative energies between different geometries is sufficient. The demands of molecular spectroscopists are typically much more stringent, and often include a detailed topographical survey of multi-dimensional
potential energy surfaces with an accuracy in the range of wavenumbers. In a benchmark study of current predictive capabilities we pick the slightly sophisticated, but conceptually simple and well studied case of the Na3 ground state, and present
a thorough investigation of the interplay between Jahn-Teller-, spin-orbit-, rovibrational- and hyperfine-interactions based
only on ab initio calculations. The necessary parameters for the effective Hamiltonian are derived from the potential energy
surface of the 12 E′ ground state and from spin density evaluations at selected geometries, without any fitting adjustments to
experimental data. We compare our results to highly resolved microwave spectra.a
a
L. H. Coudert, W. E. Ernst and O. Golonzka, J. Chem. Phys. 117, 7102–7116 (2002)
218
FA08
10:46 – 11:01
ACCURATE FIRST-PRINCIPLES SPECTRA PREDICTIONS FOR ETHYLENE AND ITS ISOTOPOLOGUES FROM
FULL 12D AB INITIO SURFACES
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THIBAULT DELAHAYE, CNRS et Universités Paris Est et Paris Diderot, Laboratoire Interuniversitaire des
Systèmes Atmosphériques (LISA), Créteil, France; MICHAEL REY, VLADIMIR TYUTEREV, Groupe de Spectrométrie Moléculaire et Atmosphérique, UMR CNRS 7331, Université de Reims, Reims Cedex 2, France; ANDREI V. NIKITIN, Atmospheric Spectroscopy Div., Institute of Atmospheric Optics, Tomsk, Russia; PETER
SZALAY, Institute of Chemistry, Eotvos University, Budapest, Hungary.
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in
Hydrocarbons such as ethylene (C2 H4 ) and methane (CH4 ) are of considerable interest for the modeling of planetary
atmospheres and other astrophysical applications. Knowledge of rovibrational transitions of hydrocarbons is of primary importance in many fields but remains a formidable challenge for the theory and spectral analysis. Essentially two theoretical
approaches for the computation and prediction of spectra exist. The first one is based on empirically-fitted effective spectroscopic models. Several databases aim at collecting the corresponding data but the information about C2 H4 spectrum present in
these databases remains limited, only some spectral ranges around 1000, 3000 and 6000 cm−1 being available. Another way
for computing energies, line positions and intensities is based on global variational calculations using ab initio surfaces. Although they do not yet reach the spectroscopic accuracy, they could provide reliable predictions which could be quantitatively
accurate with respect to the precision of available observations and as complete as possible. All this thus requires extensive
first-principles quantum mechanical calculations essentially based on two necessary ingredients: (i) accurate intramolecular
potential energy surface and dipole moment surface components and (ii) efficient computational methods to achieve a good
numerical convergence. We report predictions of vibrational and rovibrational energy levels of C2 H4 using our new ground
state potential energy surface obtained from extended ab initio calculationsa . Additionally we will introduce line positions
and line intensities predictions based on a new dipole moment surface for ethylene. These results will be compared with
previous works on ethylene and its isotopologues.
a
T. Delahaye, A. V. Nikitin, M. Rey, P. G. Szalay, and Vl. G. Tyuterev, J. Chem. Phys. 2014, 141, 104301
FA09
11:03 – 11:18
HIGH-RESOLUTION LASER SPECTROSCOPY OF S1 -S0 TRANSITION OF NAPHTHALENE: MEASUREMENT OF
VIBRATIONALLY EXCITED STATES
TAKUMI NAKANO, RYO YAMAMOTO, Graduate School of Science, Kobe University, Kobe, Japan; SHUNJI
KASAHARA, Molecular Photoscience Research Center, Kobe University, Kobe, Japan.
Naphthalene is one of the simple polycyclic aromatic molecule, and it is interesting that the excited state dynamics take
place. To understand the excited state dynamics, rotationally resolved fluorescence excitation spectra of several vibronic
bands were measured.a b In this work, we have measured high-resolution fluorescence excitation spectra across a single
mode laser and molecular beam at light angle. Vibronic bands, which lies 2866 cm −1 and 3068 cm −1 above the 0-0 band
(00 0 + 2866 cm−1 band and 00 0 + 3068 cm−1 band), were measured. Absolute wavenumber was calibrated with accuracy
0.0002 cm−1 by the measurement of Doppler-free absorption spectrum of I2 molecule and transmitting light intensity of the
stabilized etalon. Rotational lines of the 00 0 + 2866 cm−1 band were almost resolved. A part of the rotational lines were
assigned, and several energy shifts were found. On the other hand, rotational lines were not completely resolved for the 00 0
+ 3068 cm−1 band.
a
b
K. Yoshida, Y. Semba, S. Kasahara, T. Yamanaka, and M. Baba, J. Chem. Phys. 130, 19304 (2009)
H. Katô, M. Baba, and S. Kasahara, Bull. Chem. Soc. Jpn. 80, 456 (2007)
219
FA10
11:20 – 11:35
HIGH-RESOLUTION LASER SPECTROSCOPY OF THE S1 ← S0 TRANSITION OF Cl-NAPHTHALENES
SHUNJI KASAHARA, Molecular Photoscience Research Center, Kobe University, Kobe, Japan; RYO YAMAMOTO, Graduate School of Science, Kobe University, Kobe, Japan.
in
D. F. Plusquellic, S. R. Davis, and F. Jahanmir, J. Chem. Phys., 115, 225 (2001).
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High-resolution fluorescence excitation spectra of the S1 ← S0 electronic transition have been observed for 1-Cl naphthalene (1-ClN) and 2-Cl naphthalene (2-ClN). Sub-Doppler excitation spectra were measured by crossing a single-mode UV
laser beam perpendicular to a collimated molecular beam. The absolute wavenumber was calibrated with accuracy 0.0002
cm−1 by measurement of the Doppler-free saturation spectrum of iodine molecule and fringe pattern of the stabilized etalon.
For 2-ClN, the rotationally resolved high-resolution spectra were obtained for the 000 and 000 + 1042 cm−1 bands, and these
molecular constants were determined in high accuracy. The obtained molecular constants of the 000 band are good agreement
with the ones reported by Plusquellic et. al. a For the 000 + 1042 cm−1 band, the local energy shifts were found. On the other
hand, for 1-ClN, the rotational lines were not fully resolved because the fluorescence lifetime is shorter than the one of 2-ClN.
Then we determined the molecular constants of 1-ClN from the comparison the observed spectrum with calculated one.
220
FB. Spectroscopy as an analytical tool
Friday, June 26, 2015 – 8:30 AM
ar
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Chair: Christopher F. Neese, The Ohio State University, Columbus, OH, USA
FB01
CONTINUOUS MONITORING OF PHOTOLYSIS PRODUCTS BY THZ SPECTROSCOPY
8:30 – 8:45
ABDELAZIZ OMAR, ARNAUD CUISSET, GAËL MOURET, FRANCIS HINDLE, SOPHIE ELIET, ROBIN
BOCQUET, Laboratoire de Physico-Chimie de l’Atmosphère, Université du Littoral Côte d’Opale, Dunkerque,
France.
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We demonstrate the potential of THz spectroscopy to monitor the real time evolution of the gas phase concentration of
photolysis products and determine the kinetic reaction rate constanta . In the primary work, we have chosen to examine the
photolysis of formaldehyde (H2 CO) b . Exposure of H2 CO to a UVB light (250 to 360 nm) in a single pass of 135 cm length
cell leads to decomposition via two mechanisms: the radical channel with production of HCO and the molecular channel
with production of CO. A commercial THz source c (frequency multiplication chain) operating in the range 600-900 GHz
was used to detect and quantify the various chemical species as a function of time. Monitoring the concentrations of CO and
H2 CO via rotational transitions, allowed the kinetic rate of H2 CO consummation to be obtained, and an estimation of the rate
constants for both the molecular and radical photolysis mechanisms.
We have modified our experimental setup to increase the sensitivity of the spectrometer and changed sample preparation
protocol specifically to quantify the HCO concentration. Acetaldehyde was used as the precursor for photolysis by UVC
resulting in the decompositon mechanism can be described by:
CH3 CHO + hν → CH3 + HCO → CH4 + CO
Frequency modulation of the source and Zeeman modulation is used to achieve the high sensitivity required. Particular
attention has been paid to the mercury photosensitization effect that allowed us to increase the HCO production enabling
quantification of the monitored radical. We quantify the HCO radical and start a spectroscopic study of the line positions.
a
H. M. Pickett and T. L. Boyd, Chem. Phys. Lett, Vol 58, 446-449, (1978)
S. Eliet, A. Cuisset, M Guinet, F. Hindle, G. Mouret, R. Bocquet, and J. Demaison, Journal of Molecular Spectroscopy, Vol 279, 12-15 (2012).
c
G. Mouret, M. Guinet, A. Cuisset, L. Croizé, S. Eliet, R. Bocquet and F. Hindle, Sensors Journal. IEEE, Vol 13, 133 – 138, (2013)
b
FB02
MEDIUM RESOLUTION CAVITY SPECTROSCOPY FOR THE STUDY OF LARGE MOLECULES
8:47 – 9:02
SATYAKUMAR NAGARAJAN, CHRISTOPHER F. NEESE, FRANK C. DE LUCIA, Department of Physics,
The Ohio State University, Columbus, OH, USA.
It is well known that as molecules become larger the spectral lines of their high-resolution rotational spectra begin to
merge, first into modest blends, then into clusters of many lines, and finally into continua. In addition to impacting specificity,
the usual signal processing strategies used to separate spectral information from background become ineffective. Medium
Resolution Cavity Spectroscopy trades the usual excess of specificity of rotational spectroscopy for a means of obtaining
spectra of large molecules with congested or semi-continua spectra. The chief scientific question to be answered is how
large (according the several definitions of ‘large’) can a molecule be and still have structure at medium resolution. The chief
technical question to be answered is how to develop strategies to approach white noise sensitivity limits. Experimental details
and results, and theoretical results will be presented.
221
FB03
SUBMILLIMETER/INFRARED DOUBLE RESONANCE: REGIMES FOR MOLECULAR SENSORS
9:04 – 9:19
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SREE SRIKANTAIAH, Department of Physics, The Ohio State University, Columbus, OH, USA; IVAN
MEDVEDEV, Department of Physics, Wright State University, Dayton, OH, USA; CHRISTOPHER F. NEESE,
Department of Physics, The Ohio State University, Columbus, OH, USA; DANE PHILLIPS, IERUS Technologies,
Huntsville, AL, USA; HENRY O. EVERITT, Army Aviation and Missile Research Development and Engineering
Center, Redstone Arsenal, AL, USA; FRANK C. DE LUCIA, Department of Physics, The Ohio State University,
Columbus, OH, USA.
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Submillimeter/Infrared Double Resonance is a well-established technique. It has been used for spectroscopy, studies of
collisional energy transfer, and diagnostics. The high level of molecule specific spectroscopic specificity achieved through
this technique makes it an attractive candidate for sensor application. Here we will discuss its application to sensor development, with emphasis on regimes of applicability that range from mTorr to atmospheric pressure. System requirements and
development as well as theoretical and experimental results will be discussed.
FB04
9:21 – 9:36
ROTATIONAL SPECTROSCOPY AS A TOOL TO INVESTIGATE INTERACTIONS BETWEEN VIBRATIONAL
POLYADS IN SYMMETRIC TOP MOLECULES: LOW-LYING STATES v8 ≤ 2 OF METHYL CYANIDE
HOLGER S. P. MÜLLER, MATTHIAS H. ORDU, FRANK LEWEN, I. Physikalisches Institut, Universität zu
Köln, Köln, Germany; LINDA BROWN, BRIAN DROUIN, JOHN PEARSON, KEEYOON SUNG, Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, USA; ISABELLE KLEINER, Laboratoire
Interuniversitaire des Systèmes Atmosphériques (LISA), CNRS et Universités Paris Est et Paris Diderot, Créteil,
France; ROBERT SAMS, Chemical Physics, Pacific Northwest National Laboratory, Richland, WA, USA.
Rotational and rovibrational spectra of methyl cyanide were recorded to analyze interactions in low-lying vibrational
states and to construct line lists for radio astronomical observations as well as for infrared spectroscopic investigations of
planetary atmospheres. The rotational spectra cover large portions of the 36−1627 GHz region.a In the infrared (IR), a
spectrum was recorded for this study in the region of 2ν8 around 717 cm−1 with assignments covering 684−765 cm−1 .
Additional spectra in the ν8 region were used to validate the analysis.
Using ν8 datab as well as spectroscopic parameters for v4 = 1, v7 = 1, and v8 = 3 from previous studies,c we analyzed
rotational data involving v = 0, v8 = 1, and v8 = 2 up to high J and K quantum numbers. We analyzed a strong ∆v8 = ±1,
∆K = 0, ∆l = ±3 Fermi resonance between v8 = 1−1 and v8 = 2+2 at K = 14 and obtained preliminary results for two
further Fermi resonances between v8 = 2 and 3. We also found resonant ∆v8 = ±1, ∆K = ∓2, ∆l = ±1 interactions
between v8 = 1 and 2 and present the first detailed analysis of such a resonance between v8 = 0 and 1.
We discuss the impact of this analysis on the v8 = 1 and 2 as well as on the axial v = 0 parameters and compare selected
CH3 CN parameters with those of CH3 CCH and CH3 NC.
We evaluated transition dipole moments of ν8 , 2ν8 − ν8 , and 2ν8 for remote sensing in the IR.
a
b
c
Part of this work was carried out at the Jet Propulsion Laboratory under contract with the National Aeronautics and Space Administration.
M. Koivusaari et al., J. Mol. Spectrosc. 152 (1992) 377−388.
A.-M. Tolonen et al., J. Mol. Spectrosc. 160 (1993) 554−565.
222
FB05
9:38 – 9:53
VIBRATIONAL SUM FREQUENCY STUDY OF THE INFLUENCE OF WATER-IONIC LIQUID MIXTURES IN THE
CO2 ELECTROREDUCTION ON SILVER ELECTRODES
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NATALIA GARCIA REY, DANA DLOTT, Department of Chemistry, University of Illinois at UrbanaChampaign, Urbana, IL, USA.
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Understand the molecular dynamics on buried electrodes under electrochemical transformations is of significant interest.
There is a big gap of knowledge in the CO2 electroreduction mechanism due to the limitations to access and probe the liquidmetal interfaces [1,2]. Vibrational Sum Frequency Spectroscopy (VSFS) is a non-invasive and surface sensitive technique,
with molecular level detection that can be used to probe electrochemical reactions occurring on the electrolyte-electrode
interface [2]. We observed the CO2 electroreduction to CO in ionic liquids (ILs) on poly Ag using VSFS synchronized with
cyclic voltammetry. In order to follow the CO2 reaction in situ on the ionic liquid-Ag interface; the CO, CO2 and imidazolium
vibrational modes (resonant SFS) were monitored as a function of potential. We identified at which potential the CO was
produced and how the EMIM-BF4 played an important role in the electron transfer to the CO2 , lowering the CO−
2 energy
barrier. A new approach to reveal the double layer dynamics to the electrostatic environment is presented by the study of
the nonresonant sum frequency intensity as a function of the applied potential. By this method, we studied the influence of
water-ionic liquid mixtures in the CO2 electroreduction on Ag electrode. We observed a shift to lower potentials in the CO2
electroreduction in water-ILs electrolyte. Previous studies in gas diffusion fuel cells have shown the CO2 electroreduction
in a water-imidazolium–based ILs on Ag nanoparticles at lower overpotential [3]. Our VSFS study helps to understand the
fundamental electrochemical mechanism, showing how the ILs structural transition influences the CO2 electroreduction.
[1] Polyansky, D. E.; Electroreduction of Carbon Dioxide, 2014, Encyclopedia of Applied Electrochemistry, Springer
New York, pag 431-437. [2] Bain, C. D.; J. Chem. Soc., Faraday Trans., 1995, 91, 1281. [3] Rosen, B. A. et al; Science,
2011, 334 (6056), 643. Rosen, B. A. et al.; J. electrochem. Soc., 2013, 160 (2), H138.
Intermission
FB06
10:12 – 10:27
ELUCIDATING THE COMPLEX LINESHAPES RESULTING FROM THE HIGHLY SENSITIVE, ION SELECTIVE,
TECHNIQUE NICE-OHVMS
JAMES N. HODGES, BRIAN SILLERa , Department of Chemistry, University of Illinois at Urbana-Champaign,
Urbana, IL, USA; BENJAMIN J. McCALL, Departments of Chemistry and Astronomy, University of Illinois at
Urbana-Champaign, Urbana, IL, USA.
The technique Noise Immune Cavity Enhanced Optical Heterodyne Velocity Modulation Spectroscopy, or NICEOHVMS, has been used to great effect to precisely and accurately measure a variety of molecular ion transitions from species
+
+
+
bc
such as H+
It is a powerful technique,
3 , CH5 , HeH , and HCO , achieving MHz or in some cases sub-MHz uncertainty.
but a complete theoretical understanding of the complex NICE-OHVMS lineshape is needed to fully unlock its potential.
NICE-OHVMS is the direct result of the combination of the highly sensitive spectroscopic technique Noise Immune
Cavity Enhanced Optical Heterodyne Molecular Spectroscopy(NICE-OHMS) with Velocity Modulation Spectroscopy(VMS),
applying the most sensitive optical detection method with ion species selectivity.d The theoretical underpinnings of NICEOHMS lineshapes are well established,e as are those of VMS.f This presentation is the logical extension of those two preceding
bodies of work. Simulations of NICE-OHVMS lineshapes under a variety of conditions and fits of experimental data to the
model are presented. The significance and accuracy of the various inferred parameters, along with the prospect of using them
to extract additional information from observed transitions, are discussed.
a
Present Address: Tiger Optics, LLC, Warrington, PA 18976, USA
J. N. Hodges, et al. J. Chem. Phys. (2013), 139, 164201.
c
A. J. Perry, et al. J. Chem. Phys. (2014), 141, 101101.
d
K. N. Crabtree, et al. Chem. Phys. Lett. (2012), 551, 1-6.
e
F. M. Schmidt, et al. J. Opt. Soc. Amer. A (2008), 24, 1392–1405.
f
J. W. Farley, J. Chem. Phys. (1991), 95, 5590–5602.
b
223
FB07
10:29 – 10:44
CHARACTERIZATION AND INFRARED EMISSION SPECTROSCOPY OF BALL PLASMOID DISCHARGES
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SCOTT E. DUBOWSKY, Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL,
USA; BENJAMIN J. McCALL, Departments of Chemistry and Astronomy, University of Illinois at UrbanaChampaign, Urbana, IL, USA.
a
b
in
Plasmas at atmospheric pressure serve many purposes, from ionization sources for ambient mass spectrometry (AMS)
to plasma-assisted wound healing. Of the many naturally occurring ambient plasmas, ball lightning is one of the least understood; there is currently no solid explanation in the literature for the formation and lifetime of natural ball lightning. With
the first measurements of naturally occurring ball lightning being reported last year,a we have worked to replicate the natural
phenomenon in order to elucidate the physical and chemical processes by which the plasma is sustained at ambient conditions.
We are able to generate ball-shaped plasmoids (self-sustaining plasmas) that are analogous to natural ball lightning using
a high-voltage, high-current, pulsed DC system.b Improvements to the discharge electronics used in our laboratory and
characterization of the plasmoids that are generated from this system will be described. Infrared emission spectroscopy of
these plasmoids reveals emission from water and hydroxyl radical – fitting methods for these molecular species in the complex
experimental spectra will be presented. Rotational temperatures for the stretching and bending modes of H2 O along with that
of OH will be presented, and the non-equilibrium nature of the plasmoid will be discussed in this context.
Cen, J.; Yuan, P,; Xue, S. Phys. Rev. Lett. 2014, 112, 035001.
Dubowsky, S.E.; Friday, D.M.; Peters, K.C.; Zhao, Z.; Perry, R.H.; McCall, B.J. Int. J. Mass Spectrom. 2015, 376, 39-45.
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FB08
10:46 – 11:01
VUV FLUORESCENCE OF WATER & AMMONIA FOR SATELLITE THRUSTER PLUME CHARACTERIZATION.
JUSTIN W. YOUNG, CHRISTOPHER ANNESLEY, RYAN S BOOTH, JAIME A. STEARNS, Space Vehicles
Directorate, Air Force Research Lab, Kirtland AFB, NM, USA.
A quantified description of photoemission from thruster plume species, such as water and ammonia, is necessary for
complete characterization of a thruster plume. Photoemission in a plume is due to excitation of molecular species from solar
photons. For instance, electronic excitation of water with Lyman-alpha (121.6 nm) causes dissociation to the OH radical
by following one of several possible pathways. One pathway leads to an electronically excited OH radical which fluoresces
near 300 nm. Here, four-wave mixing is used to generate vacuum ultraviolet photons to excite a plume species seeded in a
jet expansion. The resulting fluorescence is analyzed and used to describe the temperature dependence of the fluorescence
signature.
FB09
REACTIONS OF 3-OXETANONE AT HIGH TEMPERATURES
11:03 – 11:18
EMILY WRIGHT, BRIAN WARNER, HANNAH FOREMAN, Department of Chemistry, Marshall University, Huntington, WV, USA; KIMBERLY N. URNESS, Department of Mechanical Engineering, University of
Colorado Boulder, Boulder, CO, USA; LAURA R. McCUNN, Department of Chemistry, Marshall University,
Huntington, WV, USA.
The pyrolysis of 3-oxetanone, O(CH2 )2 CO, has been studied in a resistively heated SiC tubular reactor at 400-1200◦ C.
Products of pyrolysis were identified via matrix-isolation FTIR spectroscopy and photoionization mass spectrometry in separate experiments. While 3-oxetanone is expected to dissociate into ketene and formaldehyde, these experiments show that
ethylene oxide and carbon monoxide are also produced. Methyl radical and ethylene were observed as additional products
and are thought to be the result of reactions involving ethylene oxide.
224
FC. Comparing theory and experiment
Friday, June 26, 2015 – 8:30 AM
Chair: Edwin Sibert, The Univeristy of Wisconsin, Madison, WI, USA
8:30 – 8:45
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FC01
VIBRATIONAL COUPLING IN SOLVATED FORM OF EIGEN PROTON
JHENG-WEI LI, KAITO TAKAHASHI, JER-LAI KUO, Institute of Atomic and Molecular Sciences, Academia
Sinica, Taipei, Taiwan.
in
The most simple solvated proton, the hydronium ion H3 O+ has been studied experimentally in its bare case as well as
with the messenger techniques. Recent studies have shown that features in the vibrational spectra can be modulated not only
by the different messengers, but also by the number of messengers. Theoretical molecular dynamics simulations have shed
some light on the H3 O+ (H2 )n clusters, but understanding on the effect of microsolvaton by the messengers toward the spectra
is still far from complete. We compare the experimental H3 O+ Arm m=1-3 spectra with accurate theoretical simulations and
oobtain the peak position and absorption intensity by solving the quantum vibrational Schrodinger equation using the potential
and dipole moment obtained from DFT methods. One of the main goals of the study is to glean into the vibrational couplings
induced by the microsolvation by the argon on the spectra region of 1500-3800 cm−1 , and to provide assignment on the peaks
observed in these regions.
8:47 – 9:02
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FC02
BINDING BETWEEN NOBEL GAS ATOMS AND PROTONATED WATER MONOMER AND DIMER
YING-CHENG LI, JER-LAI KUO, Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei, Taiwan.
H3 O+ and H5 O+
2 , Eigen and Zundel forms of the excess proton, are the basic moieties of hydrated proton in aqueous
media. Using vibrational pre-dissotion spectra, vibrational spectra of messenager-tagged species are often measured; however,
only neat species have been studied in detail by theoretical and computational means. To bridge this gap, we carry out
extensive CCSD(T)/aug-cc-pvTZ calculations to investigate the binding between commonly used noble gas (NG) messenagers
(He, Ne and Ar) with H3 O+ and H5 O+
2 to get an accurate estimate on the binding energy which yields the upper limits of
vibrational temperature of NG-tagged clusters. The binding sites of NG and low-lying transition states have also been searched
to give a better description on the energy landscape. In addition, a few exchange/correlation functionals have been tested to
access the accuracy of these methods for future and more sophisticated theoretical studies.
FC03
9:04 – 9:19
ANALYSIS OF HYDROGEN BONDING IN THE OH STRETCH REGION OF PROTONATED WATER CLUSTERS
LAURA C. DZUGAN, ANNE B McCOY, Department of Chemistry and Biochemistry, The Ohio State University, Columbus, OH, USA.
There are two types of bands in the OH stretch region of the vibrational spectra of hydrogen-bonded complexes; narrow
peaks due to isolated OH stretches and a broadened feature reflecting the OH stretches involved in strong hydrogen bonding.
This second region can be as wide as several hundred wavenumbers and is shifted to the red of the narrow peaks. In this
work we focus on H+ (H2 O)n , where n = 3 or 4.a Both of these systems exhibit a very intense, broad H-bonded band. This
breadth arises from coupling between the OH stretches and the low frequency modes. To understand the broadening observed
in the spectra, we have developed a computational scheme in which we sample displacement geometries from the equilibrium
structure based on the ground state harmonic wavefunction.b Then we combine the harmonic spectra in the OH stretch region
for each computed geometry to generate the spectrum for each protonated water structure. Based on the large anharmonicities
at play in these modes, we extend the approach using second-order perturbation theory to solve the reduced-dimensional
Hamiltonian that involves only the HOH bends and the OH stretches. This is done by expressing the normal modes used to
expand the Hamiltonian as linear combinations of internal coordinates. In this talk we will describe the approach used for
these anharmonic calculations and report preliminary results for these protonated water clusters.
a
Relph, R. A.; Guasco, T. L.; Elliot, B. M.; Kamrath, M. Z.; McCoy, A. B.; Steele, R. P.; Schofield, D. P.; Jordan, K. D.; Viggiano, A. A.; Ferguson, E. E.; Johnson, M. A.
Science, 2010, 327(5963), 308-312.
b
Johnson, C. J.; Dzugan, L. C.; Wolk, A. B.; Leavitt, C. M.; Fournier, J. A.; McCoy, A. B.; Johnson, M. A. J. Phys. Chem. A, 2014, 118, 7590-7597.
225
FC04
9:21 – 9:36
SEMIEXPERIMENTAL STRUCTURE OF THE NON-RIGID BF2 OH MOLECULE BY COMBINING HIGH RESOLUTION INFRARED SPECTROSCOPY AND AB INITIO CALCULATIONS.
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NATALJA VOGT, JEAN DEMAISON, Section of Chemical Information Systems, Universität Ulm, Ulm, Germany; AGNES PERRIN, LISA, CNRS, Universités Paris Est Créteil et Paris Diderot, Créteil, France; HANS
BÜRGER, Anorganische Chemie, Bergische Universität Wuppertal, Wuppertal, Germany.
In BF2 OH, difluoroboric acid, the OH group is the subject of a large amplitude torsion motion which induces a splitting in
the rotational spectrum as well as in the high-resolution infrared spectrum. It is interesting to check whether it is still posible
to determine a semiexperimental equilibrium structure for such a molecule. For this goal, the rotation-vibration interactions
constants have been experimentally determined by analyzing all the fondamental bands. They have also been computed ab
initio using two different levels of theory. The results of the analysis as well as the determination of the structure will be
reported.
in
FC05
9:38 – 9:48
CONFORMATIONAL, VIBRATIONAL AND ELECTRONIC PROPERTIES OF C5H3XOS (X = H, F, Cl OR Br): HALOGEN AND SOLVENT EFFECTS
MUSTAFA SENYEL, Department of Physics, Anadolu University, Eskisehir, Turkey; GUNES ESMA, Physics,
Anadolu University, Eskisehir, TURKEY; CEMAL PARLAK, Physics, Dumlupinar University, Kutahya,
TURKEY.
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The effects of halogen and solvent on the conformer, vibrational and electronic properties of thiophene-2-carbaldehyde
(C5H4OS) and thiophene-2-carbonyl-halogens [C5H3XOS; X = F, Cl or Br] were investigated employing the DFT and TDDFT methods. The B3LYP functional was used with the 6-31++G(d,p) basis set. Computations were focused on the two
conformational isomers of the compounds in the gas phase and both in a non-polar solvent and in a polar solvent. The present
work explores the effects of both the halogen and the medium on the conformational preference, geometrical parameter,
dipole moment, vibrational spectra, UV spectrum and HOMO-LUMO orbital. The findings of this work can be useful to
those systems involving changes in the conformations analogous to the compounds studied.
FC06
9:50 – 10:05
COMBINED EXPERIMENTAL AND THEORETICAL STUDIES ON THE VIBRATIONAL AND ELECTRONIC SPECTRA OF 5-QUINOLINECARBOXALDEHYDE
MUSTAFA KUMRU, MUSTAFA KOCADEMIR, TAYYIBE BARDAKCI, Department of Physics, Fatih University, Istanbul, Turkey.
Experimental and theoretical investigations have been performed on the structure, vibrational and electronic spectra of
5-quinolinecarboxaldehyde (5QC). The 4000-50 cm−1 region FT-IR and FT-Raman and the 190-1100 nm region UV–Vis
spectra of 5QC were recorded at the room temperature. Structural and spectroscopic properties of the cis and trans
conformers of 5QC were calculated by Hartree-Fock (HF) and B3LYP density functional methods using the 6-311++G(d,p)
basis set. Although calculated B3LYP frequencies are found to be closer to the experimental frequencies than the HF
calculation results, scaled frequencies of both HF and B3LYP levels are in good agreement with the experimental spectra.
The time-dependent density functional theory (TDDFT) is also used to find excitation energies, absorption wavelength,
oscillator strengths and HOMO and LUMO energies of the title molecule.
Keywords: FT-IR, FT-Raman, and UV-vis spectra; HF; DFT, HOMO-LUMO.
1.
2.
3.
4.
5.
V. Kucuk, A. Altun, M. Kumru, Spectrochim. Acta Part A 85(2012)9298.
M. Kumru, V. Kucuk, T. Bardakci, Spectrochim. Acta Part A 90(2012)2834.
M. Kumru, V. Kucuk, M. Kocademir, Spectrochim. Acta Part A, 96 (2012) 242251.
M. Kumru, V. Kucuk, P. Akyürek, Spectrochim. Acta Part A, 113 (2013) 72–79.
M. Kumru, et al., Spectrochimica Acta Part A, 134 (2015) 81–89.
This work was supported by the Scientific Research Fund of Fatih University under the project number P50011001G (1457).
226
Intermission
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FC07
10:24 – 10:39
COMBINED COMPUTATIONAL AND EXPERIMENTAL STUDIES OF THE DUAL FLUORESCENCE IN DIMETHYLAMINOBENZONITRILE (DMABN)
ANASTASIA EDSELL, STEVEN SHIPMAN, Department of Chemistry, New College of Florida, Sarasota, FL,
USA.
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The dual florescence of dimethylaminobenzonitrile (DMABN) has been investigated since the 1960s. Despite more than
50 years of previous research, the spatial configuration of the excited state causing the dual fluorescence is still controversial.
We have performed excited state calculations of DMABN in a variety of solvents of varying hydrogen-bonding affinity and
polarity using implicit solvation (COSMO-PCM) at the M06-HF level of theory, and we have also collected steady-state
absorption and fluorescence spectra of DMABN in these solvents. Our experimental spectra are broadly consistent with
previous work, and the computational results show a significant solvent dependence.
FC08
MODELING SPIN-ORBIT COUPLING IN THE HALOCARBENES
10:41 – 10:56
PHALGUN LOLUR, RICHARD DAWES, Department of Chemistry, Missouri University of Science and Technology, Rolla, MO, USA; SCOTT REID, SILVER NYAMBO, Department of Chemistry, Marquette University,
Milwaukee, WI, USA.
Halocarbenes are organic reactive intermediates with a neutral divalent carbon atom that is covalently bonded with a
halogen and another substituent. Being the smallest carbenes that exhibit closed shell ground states, they have contributed
greatly to our understanding of the reactivity of singlet carbene species and the factors that contribute to singlet-triplet energy
gaps. We report an analysis of spin-orbit coupling in the mono-halocarbenes, CH(D)X, where X = Cl, Br, I. Single Vibronic
Level (SVL) emission spectroscopy and Stimulated Emission Pumping (SEP) spectroscopy have been used to probe the
ground vibrational level structures in these carbenes which have indicated the presence of perturbations involving the lowlying triplet state. In this talk, we present two approaches to model these interactions. Anharmonic constants, singlettriplet gaps and geometry-dependent spin-orbit (SO) coupling surfaces were computed using high-level explicitly correlated
methods such as CCSD(T)-F12b and MRCI-F12. These were used to evaluate SO coupling matrix elements and hence
predict/fit mixed-perturbed singlet-triplet experimental levels. Results are also compared to those from a simpler model using
a geometry-independent SO-constant.
227
FC09
10:58 – 11:13
′
GAS-PHASE CONFORMATIONS AND ENERGETICS OF PROTONATED 2 -DEOXYADENOSINE-5′ MONOPHOSPHATE AND ADENOSINE-5′ -MONOPHOSPHATE: IRMPD ACTION SPECTROSCOPY AND THEORETICAL STUDIES
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RANRAN WU, Y-W NEI, CHENCHEN HE, LUCAS HAMLOW, Department of Chemistry, Wayne State University, Detroit, MI, USA; GIEL BERDEN, J. OOMENS, Institute for Molecules and Materials (IMM), Radboud
University Nijmegen, Nijmegen, Netherlands; M T RODGERS, Department of Chemistry, Wayne State University, Detroit, MI, USA.
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Nature uses protonation to alter the structures and reactivities of molecules to facilitate various biological functions and
chemical transformations. For example, in nucleobase repair and salvage processes, protonation facilitates nucleobase removal by lowering the activation barrier for glycosidic bond cleavage. Systematic studies of the structures of protonated
2’-deoxyribonucleotides and ribonucleotides may provide insight into the roles protonation plays in altering the nucleobase orientation relative to the glycosidic bond and sugar puckering. In this study, infrared multiple photon dissociation
(IRMPD) action spectroscopy experiments in conjunction with electronic structure calculations are performed to probe the
effects of protonation on the structures and stabilities of 2′ -deoxyadenosine-5′ -monophosphate (pdAdo) and adenosine-5′ monophosphate (pAdo). Photodissociation as a function of IR wavelength is measured to generate the IRMPD action spectra.
Geometry optimizations and frequency analyses performed at the B3LYP/6-311+G(d,p) level of theory are used to characterize the stable low-energy structures and to generate their linear IR spectra. Single point energy calculations performed
at the B3LYP/6-311+G(2d,2p) and MP2(full)/6-311+G(2d,2p) levels of theory provide relative stabilities of the optimized
conformations. The structures accessed in the experiments are determined by comparing the calculated linear IR spectra for
the stable low-energy conformers computed to the measured IRMPD action spectra. The effects of the 2′ -hydroxyl moiety are
elucidated by comparing the structures and IRMPD spectra of [pAdo+H]+ to those of its DNA analogue. Comparisons are
also made to the deprotonated forms of these nucleotides and the protonated forms of the analogous nucleosides to elucidate
the effects of protonation and the phosphate group on the structures.
228
FD. Atmospheric science
Friday, June 26, 2015 – 8:30 AM
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Chair: Kyle N Crabtree, University of California, Davis, Davis, CA, USA
FD01
8:30 – 8:45
OBSERVATION OF THE SIMPLEST CRIEGEE INTERMEDIATE CH2 OO IN THE GAS-PHASE OZONOLYSIS OF
ETHYLENE
in
CARRIE WOMACK, Department of Chemistry, MIT, Cambridge, MA, USA; MARIE-ALINE MARTINDRUMEL, Spectroscopy Lab, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA; GORDON G BROWN, Department of Science and Mathematics, Coker College, Hartsville, SC, USA; ROBERT W
FIELD, Department of Chemistry, MIT, Cambridge, MA, USA; MICHAEL C McCARTHY, Atomic and Molecular Physics, Harvard-Smithsonian Center for Astrophysics, Cambridge, MA, USA.
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Criegee intermediates (R1 R2 COO) are understood to be critical intermediates in the ozonolysis of alkenes, but their high
reactivity has traditionally made them very difficult to study directly. Although the smallest Criegee intermediates have now
been generated in the laboratory using a diiodomethane photolysis scheme, numerous questions still remain about the product
branching ratios of Criegee intermediates formed directly from ozonolysis. This talk will discuss our recent detection of the
simplest Criegee intermediate, CH2 OO, in the ozonolysis of ethylene, using Fourier transform microwave spectroscopy and
a modified pulsed nozzle. Nine other product species of the reaction were also detected, in abundances that qualitatively
support the published mechanisms and rate constants.
FD02
8:47 – 9:02
HIGH-RESOLUTION SPECTRA OF CH2 OO : ASSIGNMENTS OF ν 5 AND 2ν 9 BANDS AND OVERLAPPED BANDS
OF ICH2 OO
YU-HSUAN HUANG, LI-WEI CHEN, YUAN-PERN LEE, Applied Chemistry, National Chiao Tung University,
Hsinchu, Taiwan.
The simplest Criegee intermediate CH2 OO, important in atmospheric chemistry, has recently been detected with infrared
(IR) absorption in the reaction of CH2 I + O2 .a We have recorded high-resolution infrared spectrum of CH2 OO with rotational
lines partially resolved. In additional to derivation of some critical spectral parameters to confirm the previous assignments
of ν 3 at 1434.1 cm−1 , ν 4 at 1285.7 cm−1 , ν 6 at 909.2 cm−1 , and ν 8 at 847.4 cm−1 , the high-resolution spectra enable
us to assign with confidence the 2ν 9 at 1233.5 cm−1 and ν 5 at 1213.0 cm−1 . Observed vibrational wavenumbers, relative
intensities, and rotational structures agree well with those predicted by high-level quantum calculations. Some additional
hot bands and combination bands are also observed. We also recorded the IR spectrum of ICH2 OO under high-pressure
conditions. Observed IR intensities and vibrational wavenumbers of 1233.8 (ν 4 ), 1221 (ν 5 ), 1087 (ν 6 ), and 923 (ν 7 ) cm−1
agree with those simulated according to theoretical predictions and those observed in solid p-H2 .b The ν 4 band of ICH2 OO
interferes with the 2ν 9 band of CH2 OO even at pressure as low as 100 Torr. With direct detection of both CH2 OO and
ICH2 OO, we determined the pressure dependence of the yield of CH2 OO. The yield of CH2 OO near one atmosphere is
greater than previous reports.
a
b
Y.-T. Su, Y.-H. Huang, H. A. Witek, and Y.-P. Lee, Science 340, 174 (2013).
Y.-F. Lee and Y.-P. Lee, Chem. Phys. DOI: 10.1080/00268976.2015.1012129
229
FD03
9:04 – 9:19
DIRECT INFRARED IDENTIFICATION OF THE CRIEGEE INTERMEDIATES syn- and anti-CH3 CHOO AND THEIR
DISTINCT CONFORMATION-DEPENDENT REACTIVITY
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HUI-YU LIN, YU-HSUAN HUANG, Applied Chemistry, National Chiao Tung University, Hsinchu, Taiwan; XIAOHONG WANG, JOEL BOWMAN, Department of Chemistry, Emory University, Atlanta, GA, USA; YOSHIFUMI NISHIMURA, HENRY A WITEK, YUAN-PERN LEE, Applied Chemistry, National Chiao Tung University, Hsinchu, Taiwan.
Y.-T. Su, Y.-H. Huang, H. A. Witek, Y.-P. Lee, Science 340, 174 (2013).
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The Criegee intermediates are carbonyl oxides that play critical roles in ozonolysis of alkenes in the atmosphere. Su et al.
reported the mid-infrared spectrum of the simplest Criegee intermediate CH2 OO.a Methyl substitution of CH2 OO produces
two conformers of CH3 CHOO and consequently complicates the infrared spectrum. We report the transient infrared spectrum
of both syn- and anti-CH3 CHOO, produced from CH3 CHI + O2 in a flow reactor, using a step-scan Fourier-transform spectrometer. Guided and supported by high-level full-dimensional quantum calculations, rotational contours of the four observed
bands are simulated successfully and provide definitive identification of both conformers. Although nearly all observed bands
of anti-CH3 CHOO overlapped with syn-CH3 CHOO, the Q-branch of ν 8 near 1090.6 cm−1 is contributed solely by synCH3 CHOO, and that of ν 7 near 1280.8 cm−1 is also dominated by syn-CH3 CHOO. Furthermore, anti-CH3 CHOO shows
a reactivity greater than syn-CH3 CHOO toward NO/NO2 ; at the later period of reaction, the spectrum can be simulated
with only syn-CH3 CHOO. Without NO/NO2 , anti-CH3 CHOO also decays much faster than syn-CH3 CHOO. The direct
infrared detection of syn- and anti-CH3 CHOO should prove useful for field measurements and laboratory investigations of
the Criegee mechanism.
FD04
9:21 – 9:36
THE Ã-X̃ ELECTRONIC TRANSITIONS OF THE CH2 BrOO AND CH2 ClOO RADICALS IN THE NEAR INFRARED
REGION
NEAL KLINE, MENG HUANG, TERRY A. MILLER, Department of Chemistry and Biochemistry, The Ohio
State University, Columbus, OH, USA.
Moderate resolution cavity ring-down spectroscopy(CRDS) is used to obtain the Ã-X̃ electronic transition of the
CH2 BrOO and CH2 ClOO radicals in the near-infrared region at room temperature. The CH2 BrOO radical was generated
by 248nm excimer laser photolysis of a gas mixture of CH2 Br2 , O2 and inert gas. The CH2 ClOO radical was generated
similarly except for using CH2 ClI as the precursor. In both spectra, the first strong transition is located near 6800 cm−1 ,
and is assigned as the origin band. Several transitions are observed in the region between the origin and 9000 cm−1 . A
strong vibrational transition is observed around 800 cm−1 to the blue of the origin and attributed to the OO stretch which
is characteristic of the peroxy radical spectra. Our analysis of the vibrational structure is conducted using frequencies and
Franck-Condon factors based on electronic structure calculations. Rotational structure analyses with ab-initio calculated rotational constants and dipole moments show good agreement with the contour of the origin band. Numerous transitions around
the origin band in the CH2 BrOO radical spectrum can be explained by excitation from low-lying torsional levels in the X̃ state
that are populated at room temperature.
230
FD05
9:38 – 9:53
THE Ã-X̃ ELECTRONIC TRANSITION OF CH2 IOO RADICAL IN THE NEAR INFRARED REGION
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NEAL KLINE, MENG HUANG, TERRY A. MILLER, Department of Chemistry and Biochemistry, The Ohio
State University, Columbus, OH, USA; PHALGUN LOLUR, RICHARD DAWES, Department of Chemistry,
Missouri University of Science and Technology, Rolla, MO, USA.
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In the past few years, the photolysis of CH2 I2 in the presence of O2 has received much attention. It has been shown to be
an attractive method for producing the Criegee intermediate, CH2 O2 . Under certain conditions the reaction is also expected
to produce the iodomethyl peroxy radical, CH2 IO2 . Interestingly both species are expected to have electronic transitions in
the near infrared (NIR). The transition in CH2 O2 would be analogous to the ã − X̃ singlet-triplet transition in O3 and a NIR
Ã − X̃ transition in well-known to be characteristic of peroxy radicals. Notwithstanding the above, NIR spectra have not
been reported for either CH2 O2 or CH2 IO2 .
Based upon these considerations, we have performed the CH2 I2 photolysis with O2 in the optical cavity of our room
temperature cavity ringdown spectrometer and have discovered a spectrum in the NIR. Our recorded spectrum stretches from
a complex origin structure at ≈6800 cm−1 to beyond 9000 cm−1 . Aside from the origin its strongest feature is a similar,
complex band ≈870 cm−1 to the blue of it, which is likely an O-O stretch vibrational transition, which is present in peroxy
radicals but might also be expected for CH2 O2 . With the aid of high-level ab initio calculations (described in detail in the
subsequent talk) we have undertaken the analysis of the spectrum. We find that a spectral analysis, including a number of hot
bands arising from populated torsional levels, is consistent with the electronic structure calculations for the Ã and X̃ states of
CH2 IO2 .
FD06
9:55 – 10:10
A THEORETICAL CHARACTERIZATION OF ELECTRONIC STATES OF CH2 IOO AND CH2 OO RADICALS RELEVANT TO THE NEAR IR REGION
RICHARD DAWES, PHALGUN LOLUR, Department of Chemistry, Missouri University of Science and Technology, Rolla, MO, USA; MENG HUANG, NEAL KLINE, TERRY A. MILLER, Department of Chemistry and
Biochemistry, The Ohio State University, Columbus, OH, USA.
Criegee intermediates (R1 R2 COO or CIs) arise from ozonolysis of biogenic and anthropogenic alkenes, which is an
important process in the atmosphere. Recent breakthroughs in producing them in the gas phase have resulted in a flurry of
experimental and theoretical studies. Producing the simplest CI (CH2 OO) in the lab via photolysis of CH2 I2 in the presence
of O2 yields both CH2 OO and CH2 IOO with pressure dependent branching.
As discussed in the preceding talk, both species might be expected to have electronic transitions in the near IR (NIR). Here
we discuss electronic structure calculations used to characterize the electronic states of both systems in the relevant energy
range. Using explicitly-correlated multireference configuration interaction (MRCI-F12) and coupled-cluster (UCCSD(T)F12b) calculations we were first able to exclude CH2 OO as the carrier of the observed NIR spectrum. Next, by computing
frequencies and relaxed full torsional scans for the Ã and X̃ states, we were able to aid in analysis and assignment of the NIR
spectrum attributed to CH2 IOO.
Intermission
231
FD07
JET-COOLED LASER-INDUCED FLUORESCENCE SPECTROSCOPY OF T-BUTOXY
10:29 – 10:44
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NEIL J REILLYa , Department of Chemistry, University of Louisville, Louisville, KY, USA; LAN CHENG, JOHN
F. STANTON, Department of Chemistry, The University of Texas, Austin, TX, USA; TERRY A. MILLER, Department of Chemistry and Biochemistry, The Ohio State University, Columbus, OH, USA; JINJUN LIU, Department
of Chemistry, University of Louisville, Louisville, KY, USA.
Current address: Department of Chemistry, Marquette University.
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The vibrational structures of the Ã2 A1 and X̃ 2 E states of t-butoxy were obtained in jet-cooled laser-induced fluorescence (LIF) and dispersed fluorescence (DF) spectroscopic measurements. The observed transitions are assigned based on
vibrational frequencies calculated using Complete Active Space Self-Consistent Field (CASSCF) method and the predicted
Franck-Condon factors. The spin-orbit (SO) splitting was measured to be 35(5) cm−1 for the lowest vibrational level of the
ground (X̃ 2 E) state and increases with increasing vibrational quantum number of the CO stretch mode. Vibronic analysis of
the DF spectra suggests that Jahn-Teller (JT)-active modes of the ground-state t-butoxy radical are similar to those of methoxy
and would be the same if methyl groups were replaced by hydrogen atoms. Coupled-cluster calculations show that electron
delocalization, introduced by the substitution of hydrogens with methyl groups, reduces the electronic contribution of the
SO splittings by only around ten percent, and a calculation on the vibronic levels based on quasidiabatic model Hamiltonian
clearly attributes the relatively small SO splitting of the X̃ 2 E state of t-butoxy mainly to stronger reduction of orbital angular
momentum by the JT-active modes when compared to methoxy. The rotational and fine structure of the LIF transition to the
first CO stretch overtone level of the Ã2 A1 state has been simulated using a spectroscopic model first proposed for methoxy,
yielding an accurate determination of the rotational constants of both Ã and X̃ states.
FD08
10:46 – 11:01
NITROSYL IODIDE, INO: MILLIMETER-WAVE SPECTROSCOPY GUIDED BY AB IN IT IO QUANTUM CHEMICAL COMPUTATION
STEPHANE BAILLEUX, DENIS DUFLOT, Laboratoire PhLAM, Université de Lille - Sciences et Technologies,
Villeneuve d’Ascq, France; SHOHEI AIBA, HIROYUKI OZEKI, Department of Environmental Science, Toho
University, Funabashi, Japan.
In the series of the nitrosyl halides, XNO (where X = F, Cl, Br, I), the millimeter-wave spectrum of INO remains so far
unknown. We report our investigation on the first high-resolution rotational spectroscopy of nitrosyl iodide, INO.
One of the motivation for this work comes from the growing need in developing a more complete understanding of
atmospheric chemistry, especially halogen and nitrogen oxides chemistry that adversely impacts ozone levels. In the family
of the nitrogen oxyhalides such as nitrosyl (XNO), nitryl (XNO), nitrite (XONO), and nitrate (XON02 ) halides, those
with X = F, Cl, Br have been well studied, both theoretically and experimentally. However, relatively little is known about
the iodine-containing analogues, although they also are of potential importance in tropospheric chemistry. In 1991, the
Fourier-transform IR spectroscopic detection of INO, INO2 and IONO2 in the gas phase has been reporteda .
The INO molecule was generated by in situ mixing continuously I2 and NO in a 50-cm long reaction glass tube whose
outlet was connected to the absorption cell using a teflon tube. At the time of writing this abstract, 68 µa -type transitions
(Ka = 0 − 10), all weak, have been successfully assigned. The hyperfine structures due to both I and N nuclei will also be
presented.
S.B. and D.D. acknowledge support from the Laboratoire d’Excellence CaPPA (Chemical and Physical Properties of the
Atmosphere) through contract ANR-10-LABX-005 of the Programme d’Investissement d’Avenir.
a
I. Barnes, K. H. Becker and J. Starcke, J. Phys. Chem. 1991, 95, 9736-9740.
232
FD09
11:03 – 11:18
DISPERSED FLUORESCENCE SPECTROSCOPY OF JET-COOLED ISOBUTOXY, 2-METHYL-1-BUTOXY, AND
ISOPENTOXY RADICALS
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MD ASMAUL REZA, NEIL J REILLYa , JAHANGIR ALAM, AMY MASON, JINJUN LIU, Department of
Chemistry, University of Louisville, Louisville, KY, USA.
It is well known that rate constants of certain reactions of alkoxy radicals, e.g., unimolecular dissociation (decomposition
by C-C bond fission) and isomerization via 1,5 H-shift, are highly sensitive to the molecular structure. In the present and
the next talks, we report dispersed fluorescence (DF) spectra of various alkoxy radicals obtained under supersonic jet-cooled
conditions by pumping different vibronic bands of their B̃ ← X̃ laser induced fluorescence (LIF) excitation spectra.b,c,d This
talk focuses on the DF spectra of 2-methyl-1-propoxy (isobutoxy), 2-methyl-1-butoxy, and 3-methyl-1-butoxy (isopentoxy).
In all cases, strong CO-stretch progressions were observed, as well as transitions to other vibrational levels, including lowfrequency ones. Quantum chemical calculations were carried out to aid the assignment of the DF spectra. Franck-Condon
factors were calculated using the ezSpectrum program.e
a
Current address: Department of Chemistry, Marquette University
Wu, Q.; Liang, G.; Zu, L.; Fang, W. J. Phys. Chem A 2012, 116, 3156-3162.
Lin, J.; Wu, Q.; Liang, G.; Zu, L.; Fang, W. RSC Adv. 2012, 2, 583-589.
d
Liang, G.; Liu , C.; Hao, H.; Zu, L.; Fang, W. J. Phys. Chem. A 2013, 117, 13229- 13235.
e
V. Mozhayskiy and A. I. Krylov, http://iopenshell.usc.edu/
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FD10
11:20 – 11:35
PHOTODISSOCIATION OF METHYL ISOTHIOCYANATE STUDIED USING CHIRPED PULSE UNIFORM FLOW
SPECTROSCOPY
NUWANDI M ARIYASINGHA, LINDSAY N. ZACK, CHAMARA ABEYSEKERA, BAPTISTE JOALLAND,
ARTHUR SUITS, Department of Chemistry, Wayne State University, Detroit, MI, USA.
Chirped-Pulse Fourier-transform microwave spectroscopy has been applied in a uniform supersonic flow (Chirpedpulse/Uniform flow, CPUF) to study the 193 nm photodissociation of methyl isothiocyanate (MITC). Several products
(CH3 NC, NCS, H2 CS, HCN and HNC) were identified via their pure rotational spectra. Observation of CH3 NC and NCS
are consistent with previous studies of this system, however it is the first detection of H2 CS and HCN/HNC. Branching ratios
were obtained from these data and will be discussed.
FD11
11:37 – 11:52
DISPERSED FLUORESCENCE SPECTROSCOPY OF JET-COOLED METHYLCYCLOHEXOXY RADICALS
JAHANGIR ALAM, MD ASMAUL REZA, AMY MASON, JINJUN LIU, Department of Chemistry, University
of Louisville, Louisville, KY, USA.
Vibrational structures of the nearly degenerate X̃ and Ã states of all four positional isomers of the methylcyclohexoxy
(MCHO) radicals were studied by jet-cooled dispersed fluorescence (DF) spectroscopy, which unravels the effect of methyl
substitution at different positions on the six-membered ring. Experimentally observed vibronic transitions in the DF spectra
were assigned based on vibrational frequencies from quantum chemical calculations and predicted Franck-Condon factors
that take into account the Duschinsky rotation. DF spectra of 2-, 3-, and 4-MCHO radicals are dominated by CO-stretch
progressions or the progressions of CO-stretch modes in combination with the excited vibrational modes. DF spectra of two
lowest-energy conformers of the tertiary 1-MCHO radical, chair-axial and chair equatorial, are significantly different from
each other and from those of the other three positional isomers. Strong C-CH3 stretch progressions as well as progressions of
its combination bands with the CO stretch modes or the excited modes were observed. Such differences between the isomers
and the conformers can be explained by variation of geometry and symmetry of the electronic states of cyclohexoxy upon
methyl substitution at different positions. DF study of MCHO provides direct measurement of the energy separation between
the Ã and X̃ states that are subject to the pseudo-Jahn-Teller effect.
233
FE. Small molecules
Friday, June 26, 2015 – 8:30 AM
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Chair: Robert W Field, MIT, Cambridge, MA, USA
FE01
8:30 – 8:45
TOWARDS A GLOBAL FIT OF THE COMBINED MILLIMETER-WAVE AND HIGH RESOLUTION FTIR DATA FOR
THE LOWEST EIGHT VIBRATIONAL STATES OF HYDRAZOIC ACID (HN3 )
BRENT K. AMBERGER, R. CLAUDE WOODS, BRIAN J. ESSELMAN, ROBERT J. McMAHON, Department of Chemistry, University of Wisconsin, Madison, WI, USA.
Hydrazoic acid (HN3 ) is a near-prolate asymmetric top molecule which we have extensively studied in the millimeterwave region. Having completed an Re structure determination based on 14 isotopologues of HN3 , we have moved on to
analyze the very complex rotational spectra for the first 7 vibrationally excited states, as well as the higher K levels of the
ground vibrational state. The excited states include the 4 lowest (out of 6) fundamental modes (ν5 , ν6 , ν4 , and ν3 ) and the 3
lowest combination and overtone states (2ν5 , 2ν6 and ν5 +ν6 ). All of these states are totally symmetric (A’) except for ν6 and
ν5 +ν6 , which are antisymmetric (A”). The ro-vibrational states are substantially more intermingled than in most molecules
due to unusually wide rotational spacing in HN3 . This intermingling leads to a tangled web of perturbations connecting the
various ro-vibrational states: a-type and b-type Coriolis interactions between ν5 and ν6 , between ν4 and ν6 , and between
2ν6 or 2ν5 and ν5 +ν6 , local Fermi resonance between ν3 and 2ν6 , and a strong centrifugal distortion interaction between
the ground state and ν5 . Fortunately, we have been able to make extensive use (in both assignment of spectra and fitting of
spectroscopic parameters) of previously published high resolution FTIR data for the ν5 , ν6 , ν4 and ν3 bands and the pure
rotational spectrum of the ground vibrational state.a,b,c,d For the ground state, a-type R-branches from K = 0 to K = 9 and J
= 9 through J = 19 and b-type transitions with K = 0 through K = 2 and J values up to 56 have been assigned. The datasets
for most other states are similarly extensive. Combined millimeter-wave/FTIR multi-state fits have been performed using
Pickett’s SPFIT program.
a
J. Bendtsen, F. Hegelund and F. M. Nicolaisen, J. Mol. Spectrosc. 118, 121 (1986)
J. Bendtsen and F. M. Nicolaisen, J. Mol. Spectrosc. 119, 456 (1986)
c
d
b
234
FE02
8:47 – 9:02
MILLIMETER-WAVE SPECTROSCOPY AND GLOBAL ANALYSIS OF THE LOWEST EIGHT VIBRATIONAL
STATES OF DEUTERATED HYDRAZOIC ACID (DN3 )
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BRENT K. AMBERGER, R. CLAUDE WOODS, BRIAN J. ESSELMAN, ROBERT J. McMAHON, Department of Chemistry, University of Wisconsin, Madison, WI, USA.
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Hydrazoic acid (HN3 ) and DN3 have qualitatively different rotational spectra, owing in large part to a substantial difference in their A rotational constants (345 GHz for DN3 vs 611 GHz for HN3 ). Like HN3 , DN3 has six fundamental vibrational
modes, of which four are visible in our millimeter-wave spectra at room temperature. Between 240 and 450 GHz, many pure
rotational transitions for the ground vibrational state, ν5 (496 cm−1 ), ν6 (586 cm−1 ), ν4 (955 cm−1 ), ν3 (1197 cm−1 ), the first
overtones of ν5 and ν6 , and the combination ν5 +ν6 have been observed and assigned. Because DN3 is a light molecule, the
rotational energy levels are widely spaced, leading to numerous interactions between rotational states of different vibrational
modes. We have drawn on a wealth of previously published ro-vibrational data from high resolution FTIR spectraa,b,c,d in
our efforts to understand these perturbations. The centrifugal distortion interaction between ν5 and the ground state of DN3 is
less dramatic than in HN3 but still significant. DN3 shows the same set of Coriolis interactions as does HN3 , but again, their
magnitude is generally smaller. In DN3 the ν4 state is at slightly lower energy than 2ν5 , instead of being nearly degenerate
with ν5 +ν6 as is the case for HN3 . Therefore, there are strong local interactions between 2ν5 and ν4 , as well as between
ν3 and 2ν6 . A notable advantage in solving the DN3 problem compared to HN3 is the substantial increase in the number
and diversity of observable b-type lines in our frequency region. Furthermore, the smaller A value permits higher K states
to be observed due to a more gradual decrease in state populations. Ground state observations have been extended through
K = 11 and through J = 50. Pickett’s SPFIT has been employed to carry out multi-state fits using combined datasets of our
millimeter-wave data and the published FTIR data.
a
J. Bendtsen, F. Hegelund and F. M. Nicolaisen, J. Mol. Spectrosc. 128, 309 (1988)
d
C. S. Hansen, J. Bendtsen and F. M. Nicolaisen, J. Mol. Spectrosc. 175, 239 (1996)
b
c
FE03
9:04 – 9:19
SIMPLIFIED CARTESIAN BASIS MODEL FOR INTRAPOLYAD EMISSION INTENSITIES IN THE Ã → X̃ BENTTO-LINEAR TRANSITION OF ACETYLENE
BARRATT PARK, Department of Chemistry, MIT, Cambridge, MA, USA; ADAM H. STEEVES, Chemistry,
Ithaca College, Ithaca, NY, USA; JOSHUA H BARABAN, Department of Chemistry, University of Colorado,
Boulder, CO, USA; ROBERT W FIELD, Department of Chemistry, MIT, Cambridge, MA, USA.
The acetylene emission spectrum from the trans-bent electronically excited Ã state to the linear ground electronic X̃
state has attracted considerable attention because it grants Franck-Condon access to local bending vibrational levels of the X̃
state with large-amplitude motion along the acetylene ⇋ vinylidene isomerization coordinate. For emission from the ground
vibrational level of the Ã state, there is a simplifying set of Franck-Condon propensity rules that gives rise to only one zeroorder bright state per conserved vibrational polyad of the X̃ state. Unfortunately, when the upper level involves excitation in
the highly admixed ungerade bending modes, ν4′ and ν6′ , the simplifying Franck-Condon propensity rule breaks down—so
long as the usual polar basis (with v and l quantum numbers) is used to describe the degenerate bending vibrations of the X̃
state—and the intrapolyad intensities result from complicated interference patterns between many zero-order bright states.
We show that when the degenerate bending levels are instead treated in the Cartesian two-dimensional harmonic oscillator
basis (with vx and vy quantum numbers), the propensity for only one zero-order bright state (in the Cartesian basis) is restored,
and the intrapolyad intensities are simple to model, so long as corrections are made for anharmonic interactions. As a result
of trans ⇋ cis isomerization in the Ã state, intrapolyad emission patterns from overtones of ν4′ and ν6′ evolve as quanta
of trans bend (ν3′ ) are added, so the emission intensities are not only relevant to the ground-state acetylene ⇋ vinylidene
isomerization—they are also a direct reporter of isomerization in the electronically-excited state.
235
FE04
OBSERVATION OF LEVEL-SPECIFIC PREDISSOCIATION RATES IN S1 ACETYLENE
9:21 – 9:36
CATHERINE A. SALADRIGAS, JUN JIANG, ROBERT W FIELD, Department of Chemistry, MIT, Cambridge,
MA, USA.
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A new spectroscopic scheme was used to gain insight into the predissociation mechanisms of the S1 electronic state
of acetylene in the 47000-47300 cm−1 region. To study this mechanism, H-atom action spectra of predissociative S1 were
recorded. Instead of detecting H-atom via REMPI, an H-atom fluorescence scheme was developed, in which the H-atom
was excited to 3s and 3d levels and the fluorescence was detected. The signal-to-noise ratio of H-atom fluorescence-detected
action spectra is superior to REMPI detected H-atom spectra. By comparing the LIF and H-atom spectra, there is direct
evidence of level-dependent predissociation rates. Some of the line-widths observed in the H-atom spectra are broader than
in the LIF spectra, confirming the triplet-mediated nature of S1 acetylene.
FE05
9:38 – 9:53
FULL DIMENSIONAL ROVIBRATIONAL VARIATIONAL CALCULATIONS OF THE S1 STATE OF C2 H2
BRYAN CHANGALA, JILA, National Institute of Standards and Technology and Univ. of Colorado Department
of Physics, University of Colorado, Boulder, CO, USA; JOSHUA H BARABAN, Department of Chemistry,
University of Colorado, Boulder, CO, USA; JOHN F. STANTON, Department of Chemistry, The University of
Texas, Austin, TX, USA.
Rovibrational variational calculations on global potential energy surfaces are often essential for investigating large amplitude vibrational motion and isomerization between multiple stable conformers, as well as for understanding the spectroscopic
signatures of such dynamics. The efficient and accurate representation of high dimensional potential energy surfaces and the
diagonalization of large rovibrational Hamiltonians make these calculations a technically non-trivial task.
The first excited singlet electronic state of acetylene (C2 H2 ) is an ideal model isomerizing system. The S1 state supports
both a trans conformer and a higher energy cis conformer (Tecis − Tetrans ≈ 2700 cm−1 ), separated by a planar near-halflinear transition state (TeT S − Tetrans ≈ 5000 cm−1 ). The low-energy structure of the trans well is complicated by strong
Coriolis and Darling-Dennison interactions between the near-resonant torsion and asymmetric bending modes. The resulting
polyad patterns are eventually broken as the internal vibrational energy approaches that of the barrier to isomerization. In this
region, qualitatively new spectroscopic patterns emerge, such as rotational K-staggering and vibrational effective frequency
dips.
We examine these effects with an efficient ab initio variational treatment. Our global potential energy surface is constructed as a hybrid of a high-level reduced dimension surface, which excludes the two rCH bond lengths, and a lower-level
full dimensional surface incorporating the effects of rCH displacement. Diagonalization of the large, sparse Hamiltonian,
which contains an exact internal coordinate rovibrational kinetic energy operator, is achieved with an efficient restarted Lanczos algorithm that generates variational energies and wavefunctions. We discuss how our results elucidate the S1 state’s rich
variety of spectroscopic features and the insights they provide into the isomerization process.
Intermission
236
FE06
10:12 – 10:27
MILLIMETER-WAVE SPECTROSCOPY OF FORMYL AZIDE (HC(O)N3 )
NICHOLAS A. WALTERS, BRENT K. AMBERGER, BRIAN J. ESSELMAN, R. CLAUDE WOODS,
ROBERT J. McMAHON, Department of Chemistry, University of Wisconsin, Madison, WI, USA.
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Formyl azide (HC(O)N3 ) is a highly unstable molecule (t1/2 ∼2 hours at room temperature as a gas) that has only recently
been studied spectroscopically by UV, IR, Raman and NMR methods.ab We have synthesized formyl azide and obtained its
absorption spectrum at room temperature over the range 250-360 GHz. As in the case of carbonyl diazide,c two conformers
are expected for HC(O)N3 , with the syn-isomer 2.8 kcal/mol lower in energy than the anti-isomer (CCSD(T)/ANO1). Calculations at the same level of theory and the same basis set predict the dipole moments for the syn-isomer (µ = 1.56 D) and
anti-isomer (µ = 2.56 D). These calculations also indicate that b-type transitions should dominate the syn-isomer spectrum,
while a-type transitions become more significant in the case of the anti-isomer. Despite the anti-isomer having a larger dipole
moment, the syn-isomer still gives rise to all the dominant features of the spectrum. Thus far, five vibrational states (ν9 , ν12 ,
2ν9 , ν9 + ν12 , ν11 ) have been studied for the syn-isomer, with the highest energy state ν11 = 582.6 cm−1 . Searches for the
spectra of the anti-isomer are ongoing.
Banert, K. et al. Angew. Chem. Int. Ed. 2012, 51, 4718-4721
Zeng, X. et al. Angew. Chem. Int. Ed. 2013, 52, 3503-3506
c
Amberger, B.K. et al. J. Mol. Spectrosc. 259, (2014) 15-20
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b
FE07
MILLIMETER-WAVE ROTATIONAL SPECTRUM OF DEUTERATED NITRIC ACID
10:29 – 10:44
REBECCA A.H. BUTLER, CAMREN COPLAN, Department of Physics, Pittsburg State University, Pittsburg,
KS, USA; DOUG PETKIE, IVAN MEDVEDEV, Department of Physics, Wright State University, Dayton, OH,
USA; FRANK C. DE LUCIA, Department of Physics, The Ohio State University, Columbus, OH, USA.
Previous studies of the pure rotational spectrum of deuterated nitric acid, DNO3 , have focused on the ground and first
excited state, ν9 . This paper focuses on the next lowest energy vibrational states, covering the spectral range from 128-360
GHz. Two of them are unperturbed,ν7 and ν8 , and two of them, ν6 and 2ν9 are highly perturbed. The unperturbed states are
fit separately, while the two perturbed states are fit together using both Coriolis and Fermi interaction terms. Each state is fit
to within experimental accuracy. We also extend the assignments and update the rotational constants for ν9 .
FE08
10:46 – 11:01
THEORETICAL ANALYSIS OF THE RESONANCE FOUR-WAVE MIXING AMPLITUDES: A FULLY NONDEGENERATE CASE.
ALEXANDER KOUZOV, Department of Physics, Saint-Petersburg State University, St. Petersburg, Russia.
Degenerate (one-color) and two-color variants of the resonant four-wave mixing (RFWM) have developed into a sensitive
and nonintrusive spectroscopic tool to study molecules in different gaseous environments. Yet, the fully non-degenerate (fourcolor, 4C) RFWM was scrutinized and implemented only for the Coherent AntiStokes Raman Scattering (CARS) excitation
schemea ,b . Here, by using the line-space approachc , we analyze other 4C-RFWM schemes potentially interesting for the
efficient up- and down-frequency conversion as well as for studies of molecular states. Decoupled expressions of the 4CRFWM amplitudes are derived which allows to predict their polarization dependence.
a
b
c
B. Attal-Trétout, P. Berlemont, and J. P. Taran, Mol. Phys. 70, 1 (1990).
J.P. Kuehner, S.V. Naik, W.D. Kulatilaka, N. Chai, N.M. Laurendeau, R.P. Lucht, M.O. Scully, S. Roy, A.K. Patnaik, and J.R. Gord, J. Chem. Phys. 128, 174308 (2008).
A. Kouzov and P. Radi, J. Chem. Phys. 140, 194302 (2014).
237
FE09
11:03 – 11:18
SAND IN THE LABORATORY. PRODUCTION AND INTERROGATION OF GAS PHASE SILICATESa .
DAMIAN L KOKKIN, TIMOTHY STEIMLE, Department of Chemistry and Biochemistry, Arizona State University, Tempe, AZ, USA.
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Given its technological importance, the literature abounds with models for plasma enhanced chemical vapor deposition
of the SiH4 /O2 /Ar system. In a continuing effort to identify and characterize the optical spectra of Si3 generated in a SiH4 /Ar
pulsed discharge sourceb , we detected, via two dimensional (2D) LIF, a relatively strong electronic transition in the 570600 nm region that is strongly enhanced by the addition of a small amount of O2 . The excitation spectrum shows resolved band
structure at the pulsed laser resolution of 0.5 cm−1 and exhibits a radiative lifetime of 1.97 µs. The dispersed fluorescence
exhibits three vibrational progressions and an unusually small splitting of approximately 50 cm−1 . Here we report on efforts
to identify the molecular carrier of these bands, with particular interest paid to species resulting from oxygen impurities in
the silane discharge.
a
NSF CHE-1265885
The electronic spectrum of Si3 I: the triplet D3h system” Reilly, N. J.; Kokkin, D. L.; Zhuang, X.; Gupta, V.; Nagarajan, R.; Fortenberry, R. C.; Maier, J. P.; Steimle, T. C.;
Stanton, J. F.; McCarthy, M. C., J. Chem. Phys. 136(19), 194307, 2012.
in
b
FE10
11:20 – 11:35
IMPACT OF COMPLEX-VALUED ENERGY FUNCTION SINGULARITIES ON THE BEHAVIOUR OF RAYLEIGHSCHRÖDINGER PERTURBATION SERIES. H2 CO MOLECULE VIBRATIONAL ENERGY SPECTRUM.
Pr
el
im
ANDREY DUCHKOa , ALEXANDR BYKOV, Molecular Spectroscopy, V.E. Zuev Institute of Atmospheric Optics, Tomsk, Russia.
Nowadays the task of spectra processing is as relevant as ever in molecular spectroscopy. Nevertheless, existing techniques of vibrational energy levels and wave functions computation often come to a dead-lock. Application of standard
quantum-mechanical approaches often faces inextricable difficulties. Variational method requires unimaginable computational performance. On the other hand perturbational approaches beat against divergent series. That’s why this problem faces
an urgent need in application of specific resummation techniques. In this research Rayleigh–Schrödinger perturbation theory
is applied to vibrational energy levels calculation of excited vibrational states of H2 CO. It is known that perturbation series
diverge in the case of anharmonic resonance coupling between vibrational states [1]. Nevertheless, application of advanced
divergent series summation techniques makes it possible to calculate the value of energy with high precision (more than 10
true digits) even for highly excited states of the molecule [2]. For this purposes we have applied several summation techniques based on high-order Pade-Hermite approximations. Our research shows that series behaviour completely depends on
the singularities of complex energy function inside unit circle. That’s why choosing an approximation function modelling
this singularities allows to calculate the sum of divergent series. Our calculations for formaldehyde molecule show that the
efficiency of each summation technique depends on the resonant type.
REFERENCES
1. J. Cizek, V. Spirko, and O. Bludsky, ON THE USE OF DIVERGENT SERIES IN VIBRATIONAL SPECTROSCOPY.
TWO- AND THREE-DIMENSIONAL OSCILLATORS, J. Chem. Phys. 99, 7331 (1993).
2. A. V. Sergeev and D. Z. Goodson, SINGULARITY ANALYSIS OF FOURTH-ORDER MÖLLER-PLESSET PERTURBATION THEORY, J. Chem. Phys. 124, 4111 (2006).
a
National Research Tomsk Polytechnik University, Physics and Technology Institute, Tomsk, Russia
238
AUTHOR INDEX
ar
y
Pr
el
im
Abe, Masashi – TF02, TF03
Abeysekera, Chamara – MA04, FD10
Abramenkov, Alexander – RG08
Adam, Allan G. – TA03, TA07
Agarwal, Ankur – TE09
Agarwal, Jay – TH06
Ahmed, Musahid – WG05, RB05
Ahn, Ahreum – TD06, TD07
Aiba, Shohei – FD08
Akmeemana, Anuradha – MG07
Al-Refaie, Ahmed Faris – MH04,
MH13
Alam, Jahangir – FD09, FD11
Aldridge, Leland M. – RJ03
Alekseev, E. A. – WF12
Allison, Thomas K – TF07
Allodi, Marco A. – TF10, TF11, TI09,
TI10, RH09, RI03, RI14
Alonso, José L. – TG06, TG08
Amano, Takayoshi – MI04, RD05,
RD06, RD07
Amberger, Brent K. – MG09, MG10,
FE01, FE02, FE06
Amicangelo, Jay – RJ14
Amiot, Claude S. – MJ07
AMYAY, Badr – TB06
ANDERS, CATHERINE B – RC09
Anderson, David T. – RJ05
Annesley, Christopher – RG10, FB08
Antonov, Ivan – WG12
Appadoo, Dominique – TB07, WG09
Araki, Mitsunori – RI09
Arce, Héctor – WI14
Archer, Kaye A – WH14
Ard, Shaun – RA06
Ariyasingha, Nuwandi M – MA04,
FD10
Armacost, Michael D. – TE09
Armentrout, Peter – RA06
Arnold, Sean – RC07
Arsenault, E. A. – MG05, RH13
Arunan, Elangannan – RB10
Asselin, Pierre – RB10
Asvany, Oskar – MI01, RB03, RJ01
Aviles Moreno, Juan-Ramon – RF14,
RF15
B
Bagdonaite, Julija – MF01
Bailey, Jeremy – MH09
Bowman, Joel – FD03
Brageot, Emily – TE03
Brathwaite, Antonio David – RA09
Bray, Caitlin – RF01, RF02, RH13
Brice, Joseph T. – TH05, WA01
Brinker, Katelyn R. – RC02
Brister, Matthew M – TI05
Broderick, Bernadette M. – TH06,
RJ07, RJ09
Brooke, James S.A. – RD10
Brown, Gordon G – TE08, RC07,
FD01
Brown, James – RG02
Brown, Linda – MH05, MJ11, MJ14,
TG01, TG02, FB04
Bruneau, Yoann – TJ05
Brünken, Sandra – MI01, RB03, RJ01
Bucchino, Matthew – RA01
Buckingham, Grant – WG05
Bui, Thinh Quoc – RE05, RF01, RF02
Buma, Wybren Jan – RI04
Bürger, Hans – FC04
Burkart, Johannes – TF06
Burkhardt, Andrew – WI04
Burrmann, Nicola J. – RJ13
Butler, Rebecca A.H. – FE07
Bykov, Alexandr – FE10
in
A
Bailey, Josiah R – TG14
Bailleux, Stephane – RD04, FD08
Bakker, Daniël – WG03, RB02
Balabanoff, Morgan E. – RJ05
Banerjee, Pujarini – WJ10, WJ11,
WJ12
Bao, Xun – MI12, MI14
Baraban, Joshua H – TH11, TJ09,
RD12, RG14, FE03, FE05
Bardakci, Tayyibe – FC06
Barnum, Timothy J – TJ06, TJ07,
TJ09
Bartlett, Joshua – RA06, FA05
Basterretxea, Francisco J. – WA02,
RF11
Baudhuin, Melissa A. – TA10, RA10
Baumann, Esther – WF07
Beale, Christopher A. – MH10
Bell, Aimee – WG10
Belloche, Arnaud – RI05, RI06
Belov, Sergey – WF12
Benidar, Abdessamad – MH11
Benke, Kristin – RE01
Benner, D. Chris – MH05, MJ11,
RF02, RF08
Bensiradj, Nour el Houda – RH14
Berden, Giel – MI13, WG02, RB04,
FC09
Bergin, Edwin – WI08
Bermúdez, Celina – TG06
Bernath, Peter F. – MH09, MH10,
TB07, RD10
Betz, Thomas – MG11, TD02
Bevan, John W. – WJ04, WJ08
Bhatta, Ram – RG06
Białkowska-Jaworska, Ewa – RF11
Billinghurst, Brant E – TB03, TB07,
RB06
Binns, Marshall – RA01
Bird, Ryan G – TG14
Bittner, Dror M. – RA04, RH04, RH05
Bjork, Bryce J – WF02
Blake, Geoffrey – TF10, TF11, TI09,
TI10, WI13, RC01, RH08,
RH09, RI03, RI14
Bocklitz, Sebastian – TD11
Bocquet, Robin – FB01
Boopalachandran, Praveenkumar –
RA10
Booth, Ryan S – RG10, FB08
Booth, S. Tom – WI04
Böttcher, Fabian – TJ12
Boudon, Vincent – TB06, RE06
Bowen, K P – WG06
Bowen, Kit – MI15
C
Caballero-Mancebo, Elena – TD05
Cairncross, William – MF11
Caminati, Walther – RH06
Campbell, Ian – RJ14
Candian, Alessandra – RI04
Cao, Wenjin – MI10, MI11, RA11
Carlotti, Massimo – RF10
Carlson, Michaela – RE01
Carollo, Ryan – TJ05
Carrat, Vincent – TJ03
Carrington, Tucker – RG02, RG03
Carroll, Brandon – TF10, TF11, WI04,
WI12, WI13, RC01, RH08,
RH09, RI03, RI14
Carter, Jason P – WG09
Case, Amanda – TI12
Casey, Sean M. – TA10
Cernicharo, Jose – RD08, RI07
Chakraborty, Tapas – WJ10, WJ11,
WJ12
Chan, MAN-CHOR – TA05
Chang, M.-C. Frank – TE03
Changala, Bryan – TH11, WF02,
RD12, FE05
Chen, Li-Wei – FD02
239
D
Dagdigian, Paul – MF07
Dahlstrom, Julie – RI08
Dai, HAI-LUNG – TI14, RE08
Daily, John W – WG05, RB05
Daly, Adam M – TE03, TG01, TG02,
TG03, TG06, RD07
Daly, Ryan W – TE01
Eden, J. Gary – MJ05, MJ08
Edsell, Anastasia – FC07
Eibl, Konrad – TG12
Eidelsberg, Michele – RD09
Eliet, Sophie – FB01
Elliott, Ben – RD07
Ellison, Barney – WG05, RB05
Emerson, N J – WI01
Endo, Yasuki – RH07
Endres, Christian – RB07, RB08
Erickson, Trevor J. – MJ06, RF09
Ernst, Wolfgang E. – FA02, FA07
Escribano, Rafael – RI12
Esma, Gunes – FC05
Esselman, Brian J. – MG09, MG10,
FE01, FE02, FE06
Evans, Corey – MF13, WG09
Everitt, Henry O. – FB03
Ewing, Paul R. – TE09
Eyler, Edward E. – TJ05, RJ03
in
ar
y
Dantus, Marcos – TI02
Dattani, Nikesh S. – MF08, MF09,
MF10, MJ07
Davis, Benjamin G. – WA02
Dawadi, Mahesh B. – RG06
Dawes, Richard – WA03, FC08, FD05,
FD06
De Lucia, Frank C. – TE01, TE09,
TG08, RI01, FB02, FB03, FE07
de Oliveira, Nelson – WG07, WG08,
RD09
de Vries, Xander – RI14
Dean, Jacob C. – RG01
DeBlase, Andrew F – WH14
Delahaye, Thibault – RF05, FA08
Delcamp, Jared – WJ13
Delvin, Jack – TA04
Demaison, Jean – MG04, TG04, FC04
DePalma, Joseph W – MI08
Deprince, Bridget Alligood – WA04
Devasher, Rebecca – RC06
Devi, V. Malathy – MH05, MJ11,
RF02, RF08
Dewberry, Chris – TE02, RF12, RF13,
RH01, RH02
Diddams, Scott – WF07
DiScipio, Regina – TI06
Dixneuf, Sophie – RE09
Dlott, Dana – FB05
Dobrev, Georgi – TF09
Dollhopf, Niklaus M – WI12, WI13
Dolson, David A – TC06, RC09
Domenech, Jose Luis – RD08
Doney, Kirstin D – RG09
Dorris, Rachel E. – MG08
Douberly, Gary E. – TH04, TH05,
TH06, WA01, WA06, RJ07,
RJ08, RJ09
Doyle, John M. – WF02, FA06
Drouin, Brian – TE03, TG01, TG02,
TG06, RD06, RD07, RF02,
FB04
Dubowsky, Scott E. – FB07
Duchko, Andrey – FE10
DUCOURNEAU, Gaël – TB05
Duffy, Erin M. – MI06
Duflot, Denis – FD08
Dulick, Michael – MH09, MH10
Dumont, Elise – TI08
Duncan, Michael A – RA09, RE04,
RG12, RG13
Dupré, Patrick – MJ10, WF10
Dzugan, Laura C. – FC03
Pr
el
im
Chen, Ming-Wei – TH09
Chen, Wang – MJ01
Chen, Wenting Wendy – MJ05
Chen, Yuning – TF07
Cheng, Cunfeng – WF05
Cheng, Lan – TH01, RA08, FD07
Cheng, Wang-Yau – TF12
Cheung, Allan S.C. – TA05
Chew, Kathryn – TI11
Cho, Young-Sang – MF08
Choi, Myong Yong – TD06, TD07
Choi, Yoon Jeong – MG05, RC04
Chow, C S – MI12
Christensen, Lance – RE05
Christopher, Casey – TA09
Cich, Matthew – WF08, WF09
Cocinero, Emilio J. – TD05, WA02,
RF11
Codd, Terrance Joseph – TH09
Coddington, Ian – WF07
Cohen, Michael – WH08
Colvin, Sean – TD09
Cooke, S. A. – MG05, RC04, RH12
Coplan, Camren – FE07
Corby, Joanna F. – WI11
Cornell, Eric – MF11, MF12
Corral, Inés – TI04
Cossel, Kevin – MF11, MF12
Coudert, L. H. – WF11, WJ04, RF04
Cox, Richard M – RA06
Coy, Stephen – TJ08, TJ09
Crabtree, Kyle N – MG01, TE08
Craig, Norman C. – MG04, TC09,
RC05
Craig, Stephanie – MI09
Craver, Barry – TE09
Crawford, Timothy J – MH05, MJ14,
RD07
Crespo-Hernández, Carlos E. – TI04,
TI05, TI06
Crim, Fleming – TI12
Crockett, Nathan – WI10, WI13
Crozet, Patrick – TF09
Cubel Liebisch, Tara – TJ12
Cueto, Maite – RD08
Cuisset, Arnaud – TB05, WG11, FB01
Cummins, Christopher – MJ06
E
Ecija, Patricia – TD05, WA02, RF11
F
Fan, Lin – MI13
Faucheaux, Jacob A – RG05
Faye, Mbaye – TB06
Federman, Steven – WI05, RD09
Feifel, Raimund – WG03
Fermann, Martin – TF05, WF06
Fernández, José A. – WA02
Fernandez-Lopez, Manuel – WI14
Field, Robert W – MA04, MJ06,
MJ13, TJ06, TJ07, TJ08, TJ09,
RF09, FD01, FE03, FE04
Finneran, Ian A – TF10, TF11, TI09,
TI10, RC01, RH08, RH09
Fischer, Theo – RJ10
Flagey, Nicolas – WI05
Flaud, Jean-Marie – TG04, RF10
Fleisher, Adam J. – WF01, WF04,
RF03
Folkers, T W – WI01
Foltynowicz, Aleksandra – TF05,
TF08
Forbes, D – WI01
Foreman, Hannah – FB09
Forthomme, Damien – MF07, WF09
Fortman, Sarah – TG08, RI01
Fournier, Gilles – WG11
Fournier, Joseph – MI08, MI09, TD09,
WJ09
Frank, Derek S. – RH11, RH12
Freund, R W – WI01
Friedel, Douglas – WI11, WI15
Fu, Dejian – RF07
Fujita, Chiho – MH14
Fujiwara, Takashige – TI03
240
H
Habgood, Matthew – RH05
Haenni, Benjamin C. – MG10, TI12,
RJ13
Halfen, DeWayne T – WI01, RA02
Hall, Gregory – MF07, TI13, WF08,
WF09
Hall, Taylor M – TE08, RC07
Hamlow, Lucas – MI13, MI14, FC09
Hammer, Nathan I – MI15, WJ13
Harada, Kensuke – RH07
Hargreaves, Robert J. – MH09, MH10,
TB07
Harms, Jack C – MJ04
Harris, Robert J – WI14
Hauser, Andreas W. – FA02, FA07
Havenith, Martina – MA03, RJ10
Hays, Brian – TE04, TE05, TH03,
WA04
He, Chenchen – MI12, MI13, MI14,
FC09
Heaven, Michael – TA06, RA06,
FA03, FA04, FA05
Heays, Alan – WG08, RD09
Heckl, Oliver H – WF02
Heikal, Ahmed A – TI01
Heim, Zachary N. – MG09
Helal, Yaser H. – TE09
Hemberger, Patrick – RB05
Hemmers, O – WG06
Hepburn, John – TC02
Hermes, Matthew – RG04
Hernandez, Federico J – TH05, WA01
Herrero, Victor Jose – RD08, RI10,
RI12
Hewett, Daniel M. – MG13, TH08,
RG11
Hill, Christian – MH01, MH02, MH03
Hindle, Francis – TB05, FB01
Hirata, So – RG04, RG05
Pr
el
im
GABARD, Tony – TB06
Gaigeot, Marie-Pierre – RB02
Galica, Scott E. – RJ03
Gallagher, Tom – TJ02, TJ03, TJ04
Galvin, Thomas C. – MJ05
Gamache, Robert R. – MH06, MJ11
Gans, Berenger – WG07
Gao, Jiao – TG11
Gao, Juehan – MI12, MI14, RB04
Garand, Etienne – MI06, MI07, TD10
Garavelli, Marco – TI08
Garcia Rey, Natalia – FB05
Gardner, Adrian – FA04
Garrod, Robin T. – RI05
Gaster, Sydney A – TE08, RC07
Gato-Rivera, Beatriz – MF03
Gauss, Jürgen – TD01, RA08
Gavilan, Lisseth – RD09
Geballe, Thomas R. – WI07
Gellman, Samuel H. – TD08
Georges, Robert – MH11, TB01,
RB10, RE06
Ghosh, Supriya – TD04
Gibson, Bradley M. – RE07
Giorgetta, Fabrizio – WF07
Gipson, Courtney N – MJ04
Giuliano, Barbara Michela – TD02,
RH06
Giussani, Angelo – TI08
Gnanasekar, Sharon Priya – RB10
Goldshlag, William – MJ08
Goldsmith, Paul F – WI05
GOLUBIATNIKOV, G Yu – WF12
Gong, Justin Z – TI15
González, Leticia – TI04
Good, Jacob T – TF10, TF11
Gord, Joseph R. – MG13
Gordon, Iouli E – MH01, MH02,
MH03, RD10
Gorlova, Olga – TD09
Goto, Miwa – WI07
Gottlieb, Carl A – RD12
Gou, Qian – RH06
Goubet, Manuel – RB10
Goudreau, E. S. – TA07, TB04
Gould, Phillip – TJ05
Grabow, Jens-Uwe – MA02, WF11
Grames, Ethan M – MJ04
Grant, Mikayla L. – MG07
Grau, Matt – MF11
Gray, Jeffrey A. – RC03
Green, Susan – TE02
Greene, C. H. – TJ12
Hirota, Eizi – TH13, RH03
Hobbs, L. M. – RI08
Hodges, James N. – MF05, MF06,
FB06
Hodges, Joseph – WF01, WF03,
WF04, RF02, RF03, RF05
Hofferberth, Sebastian – TJ12
Holland, Daniel – TF10, TF11
Holt, Jennifer – TE01
Hoo, Jiajun – RF02
Hopkins, Scott – TC02, RB01
Horrocks, Benjamin R – RC08
Hougen, Jon T. – TG07, TG13, WF12
Houlahan, Jr., Thomas J. – MJ05
Hsu, Yen-Chu – TF12, WH02
Hu, Shui-Ming – WF05
Huang, Dao-Ling – RG15
Huang, Meng – TG05, FD04, FD05,
FD06
Huang, Wenyuan – WJ02
Huang, Xinchuan – MH06
Huang, Yu-Hsuan – FD02, FD03
Huet, T. R. – WF11, RB10, RF14,
RF15
Huff, Anna – RH02
Hull, Alexander W. – MJ06, RF09
Hunt, Katharine – MJ09
ar
y
G
Gresh, Dan – MF11, MF12
Grimes, David – TJ06, TJ07, TJ08,
TJ09
Groenenboom, Gerrit – MJ09
Groner, Peter – MG04, TG01, TG02,
TG04
Grubbs II, G. S. – RC02, RC10, RH12
Gruet, Sébastien – WG11, RB07,
RB08
Gu, Qun Jane – TE03
Guillemin, J.-C. – RI02, RI06, RI07
Guillemin, R – WG06
Gupta, Harshal – WI09, WI10
Gurusinghe, Ranil M. – TG09, TG10
Gutle, C. – WF11
in
Fukushima, Masaru – MJ12, TH12
I
Ichino, Takatoshi – TH01
Ilyushin, V. – WF12
Indriolo, Nick – WI08
Inomata, Risa – WH05
Ioppolo, Sergio – RI03, RI14
Ishikawa, Haruki – WH05, WH06,
WH12, WH13
Ishiwata, Takashi – MJ12, TH13
Ito, Kenji – WG07
Ivanov, Maxim – WJ07
Iwakuni, Kana – TF02
J
Jäger, Wolfgang – TC08, TD04, TG11,
WJ02, WJ03
Jaiswal, Vishal K. – TI08
Jang, Heesu – MG03
Janik, Ireneusz – TH14
Jansen, Paul – TJ01
Jawad, Khadija M. – TH08
Jenkins II, Paul A. – MF05, MF06
Jensen, Per – MI02
Jian, Tian – RH15
Jiang, Jie – WF06
Jiang, Jun – MJ06, MJ13, RF09, FE04
241
Pr
el
im
Ka, Soohyun – MG03
Kanamori, Hideto – RJ06
Kang, Hyuk – MI05
Kang, Justin M. – MG07
Kaniecki, Marie – TI02
Kannengießer, Raphaela – TG12
Karman, Tijs – MJ09
Kasahara, Shunji – TH13, FA09, FA10
Kasahara, Yasutoshi – WH06, WH12,
WH13
Kassi, Samir – MH11, TF06, RE06
Kaufmann, Matin – RJ09, RJ10
Kawaguchi, Kentarou – MJ01
Kawasaki, Hiroyuki – RJ06
Kawasaki, Takayuki – WH05
Kawashima, Yoshiyuki – RH03
Keel, S C – WI01
Kelleher, Patrick J – MI08
Kelly, John T. – MI15
Kern, Jeffrey S. – WI15
Khan, Nazir D. – WJ05
Khodabakhsh, Amir – TF05, TF08
Kidwell, Nathanael – RG01
Kim, Jihyun – MG03
Kim, Jongjin B. – TH01
Kim, JungSoo – RA06
Kim, Rod M. – TE03
Kimutai, Bett – MI12
King, Adrian – RH05
Kingsley, J – WI01
Kisiel, Zbigniew – TB02, TG08, RF11
Kleinbach, Kathrin Sophie – TJ12
Kleiner, Isabelle – TG13, FB04
Klemperer, William – RH11
Kline, Neal – FD04, FD05, FD06
Klose, Andrew – WF07
Kluge, Lars – MI01
Knee, Joseph L. – RH13
Knezz, Stephanie N. – RJ13
Kobayashi, Kaori – MH07, MH14
Kocademir, Mustafa – FC06
Kochanov, Roman V – MH01, MH02,
MH03
Leicht, Daniel – RJ10
Lemaire, Jean Louis – RD09
Leonov, Igor I – WJ04
Leopold, Doreen – TA10, RA10
Leopold, Ken – TE02, RF12, RF13,
RH01, RH02
Lesarri, Alberto – TD05, WA02
Lesslie, Michael – WG02
Leung, Helen O. – TC03, WJ05, WJ06
Leung, Tong – TC02
Lewen, Frank – RB07, RB08, RD02,
RD03, FB04
Lewis, Brenton R – WG08
Li, Biu Wa – TA05
Li, Gang – RD10
Li, Jheng-Wei – FC01
Li, Ying-Cheng – FC02
Li Chun Fong, Lena C. M. – MF09
Liebermann, Hans P. – TJ13, TJ14
Lin, Hui-Yu – FD03
Lin, Ming-Fu – RE01
Lin, Wei – RH10, RH12
Lin, Yen-Wei – RJ02
Lin, Zhou – MI03
Lindle, D W – WG06
Linnartz, Harold – RG09
Linton, Colan – TA03, TA07
Liu, An-Wen – WF05
Liu, Jinjun – TI07, FD07, FD09, FD11
Liu, Qingnan – WF04
Liu, Tze-Wei – TF12
Liu, Xunchen – WJ02
Liyanage, Nalaka – WJ13
Lodi, Lorenzo – TA08
Lolur, Phalgun – FC08, FD05, FD06
Long, B. E. – MG05
Long, David A. – WF01, WF04, RF02
Looney, Leslie – WI11, WI14, WI15
Lopez, Gary – RH15
Louviot, Maud – RE06
Löw, Robert – TJ12
Lozovoy, Vadim V. – TI02
Lu, Xin – RH10
Lu, Yan – WF05
Lucchese, Robert R. – WJ04, WJ08
Lucht, Robert P. – RE02, RE03
Lunny, Elizabeth M – RF01, RF02
Lyons, James R – RD09
ar
y
K
Kocheril, G. Stephen – MF05, MF06
Koeppen, Nicole – WI06, RE07
Kokkin, Damian L – TA01, TA02,
TA04, RA07, FA06, FE09
Kolesniková, Lucie – TG08
Kolomenskii, Alexander – RF06
Konar, Arkaprabha – TI02
Konder, Ricarda M. – TA03
Kondo, Makoto – WH06
Korn, Joseph A. – TH08, RG11
Kouzov, Alexander – FE08
Kowzan, Grzegorz – TF05, WF06
Kozyryev, Ivan – FA06
Kregel, Steven J. – TD10
Krim, Lahouari – RI11
Krin, Anna – TE06, TE07
Krishnan, Mangala Sunder – TC10
Kubasik, Matthew A. – MG13
Kumari, Sudesh – MI11
Kumru, Mustafa – FC06
Kuo, Jer-Lai – FC01, FC02
Kurusu, Itaru – WH13
Kusaka, Ryoji – WH10, WH11
Kwabia Tchana, F. – TB06, TG04,
RB09
in
Jiménez-Redondo, Miguel – RI10
Joalland, Baptiste – MA04, FD10
Johanssson, Alexandra C – TF05,
TF08
Johnson, Britta – TH02
Johnson, Christopher J – MI08
Johnson, Mark – MI08, MI09, TD09,
WH14, WJ09
Jordan, Kenneth D. – WH14
Joyeux, Denis – WG07, RD09
Jusko, Pavol – RB03
L
Laane, Jaan – MG05
Laas, Jacob – WA04
Lach, Grzegorz – MF09
Lackner, Florian – FA02
Lafferty, Walter – TG04
Lambrides, E. – WI07
LAMPIN, Jean François – TB05
Langer, William D – WI05
Lapinov, Alexander – WF12
Le, Anh T. – TI13
Le Roy, Robert J. – MF08, MF09,
MF10, MF13, MJ02, MJ03,
MJ07, TC02, RJ04
Leavitt, Christopher M. – TH05,
WA01
Lee, Chien-Chung – WF06
Lee, Chun-Woo – TJ10
Lee, Jeonghun – TJ04
Lee, Katherine – WI14
Lee, Kelvin – MG02
Lee, Kevin – TF05, WF06
Lee, Sang – TH07
Lee, Timothy – MH06
Lee, Yuan-Pern – FD02, FD03
Lees, Ronald M. – TB03
Lefebvre-Brion, H. – TJ13, TJ14
Legon, Anthony – WJ01, RA03,
RA04, RA05, RH04
Lehmann, Kevin – MH12
M
Ma, Jianqiang – TI14
MacDonald, Michael A – WG04
Mackenzie, Becca – TE02, RF12,
RF13, RH01, RH02
Magnuson, Eric – TJ03
Mahé, Jérôme – RB02
242
Nemchick, Deacon – WH08
Nenov, Artur – TI08
Neumark, Daniel – TH01
Newbury, Nathan R. – WF07
Nguyen, Ha Vinh Lam – MG06,
TD03, TG07, TG12
Nguyen, Trung – FA06
Nickerson, Nicole M. – TA03
Nikitin, Andrei V. – MJ14, FA08
Nishimiya, Nobuo – MJ02, MJ03
Nishimura, Yoshifumi – FD03
Nishiyama, Akiko – TF04
Niu, Ming Li – MF02, WG08
Nourry, Sendres – RI11
Novick, Stewart E. – RH10, RH11,
RH12, RH13
Nunkaew, Jirakan – TJ02
Nyambo, Silver – FC08
in
ar
y
Medvedev, Ivan – TG08, FB03, FE07
Melko, Joshua J. – RA06
Melnik, Dmitry G. – TH09
Menges, Fabian – MI09
Menten, Karl M. – WI10, RI05
Merer, Anthony – WH02
Merkt, Frederic – TJ01
Merrill, W G – TI12
Mescheryakov, A. A. – WF12
Mesko, AJ – RI13
Messinger, Joseph P. – WJ06
Milam, Stefanie N – RI13
Miliordos, Evangelos – MJ09, WJ09,
RG12
Miller, Scott – TD09
Miller, Terry A. – TG05, TH09, TH10,
FD04, FD05, FD06, FD07
Min, Ahreum – TD06, TD07
Minei, A. J. – RC04
Mironov, Andrey E. – MJ08
Misono, Masatoshi – TF04
Mizoguchi, Asao – RJ06
Moazzen-Ahmadi, Nasser – WH01
Mohr, Christian – WF06
Moon, Cheol Joo – TD06, TD07
Moradi, Christopher P. – TH04, TH05,
TH06, RJ07, RJ08
Moriwaki, Yoshiki – MH07, MI04
Mormile, Melanie R. – RC02
Morris, Patrick – WI09, WI10
Morville, Jérôme – TF09
Motiyenko, R. A. – RF14, RF15, RI02,
RI06, RI07
Mouret, Gaël – TB05, WG11, FB01
Muenter, John – TC04
Mukamel, Shaul – TI08
Mullaney, John Connor – WJ01, RH05
Müller, Holger S. P. – RD03, RI05,
RI06, FB04
Mundy, Lee – WI14, WI15
Muscarella, Seth – TA01
Mutunga, Fredrick M. – RJ05
Pr
el
im
Mai, Sebastian – TI04
Maltseva, Elena – RI04
Manceron, Laurent – TB06, TG04,
RB09
Maner, Jon – RE04, RG13
Mani, Devendra – RJ10
Mantz, Arlan – MH05, MJ11, MJ14,
TG01, TG02
Margulès, L. – RI02, RI06, RI07
Markus, Charles R. – MF05, MF06
Marlett, Melanie L. – MI03
Marquetand, Philipp – TI04
Marsh, Brett – MI06, MI07, TD10
Marshall, Frank E – RC02
Marshall, Mark D. – TC03, WJ05,
WJ06
Martin-Drumel, Marie-Aline – MG01,
TB02, TE08, RB07, RB08,
RD12, FD01
Martı́nez-Fernández, Lara – TI04
Mascaritolo, Kyle – FA03, FA04
Mase, Takayuki – RH03
Maslowski, Piotr – TF05, WF06
Mason, Amy – FD09, FD11
Maté, Belén – RI10, RI12
Matsuba, Ayumi – TF04
Matsushima, Fusakazu – MH07, MI04
MATSUSHITA, Yuki – RI09
Matthews, Devin A. – TI15, RA08
Mauney, Daniel – RE04, RG13
Maxwell, Stephen E – RF05
McBurney, Carl – TD08
McCall, Benjamin J. – MF04, MF05,
MF06, WI06, RE07, FB06, FB07
McCarthy, Michael C – MG01, MG02,
TD01, TE08, RB07, RB08,
RD12, FD01
McCaslin, Laura – RJ07
McColl, M – WI01
McCoy, Anne B – MI03, TG05,
WH07, FC03
McCunn, Laura R. – FB09
McDonald II, David C – RG13
McElmurry, Blake A. – WJ04
McEwen, Bridget C. – RD11
McGuire, Brett A. – WI12, WI13,
RI03, RI14
McKellar, Bob – WH01, RB06
McMahon, Robert J. – MG09, MG10,
TI12, RJ13, FE01, FE02, FE06
McMahon, Terry – RB01
McMahon, Timothy J – TG14
McMillan, James P. – RI01
McNamara, Louis E. – WJ13
McNaughton, Don – WG09
McRaven, C. – WF08
Medcraft, Chris – MG11, TE07
N
Nagarajan, Satyakumar – FB02
Nagy, Zsofia – WI09, WI10
Nahon, Laurent – WG07
Nairat, Muath – TI02
Nakajima, Masakazu – RH07
Nakano, Takumi – FA09
Nakashima, Kazuki – TF04
Nava, Matthew – MJ06
Neese, Christopher F. – TE01, TE09,
RI01, FB02, FB03
Nei, Y-W – MI12, FC09
Nelson, Rebecca D. – MG07
O
O’Brien, James J – MJ04
O’Brien, Leah C – MJ04
Obenchain, Daniel A. – RH10, RH11,
RH12, RH13
Ocola, Esther J – MG05
Odom, Brian C. – RJ02
Oh, JUNG JIN – MG03
Oishi, Ryo – MI04
Oka, Takeshi – WI07, RI08
Okumura, Mitchio – MA01, RE05,
RF01, RF02
Olinger, Aaron C – TE10
Omar, Abdelaziz – FB01
Ono, Shuhei – RF09
Oomens, J. – MI12, MI13, MI14,
WG02, RB03, RB04, RI04,
FC09
Ooms, Kristopher J – TC05
Opoku-Agyeman, Bernice – WH07
Ordu, Matthias H. – RD03, FB04
Ormond, Thomas – RB05
Orphal, Johannes – RE09
Osburn, Sandra – WG02
Ossenkopf, Volker – WI09, WI10
Ouamerali, Ourida – RH14
Ozeki, Hiroyuki – MH14, RD04,
FD08
P
Panchenko, Yurii – RG08
Pandit, Bill – TI07
Park, Barratt – MA04, MJ13, RF09,
FE03
Parks, Deondre L – TE08
243
R
Radi, Peter – FA01
Rathore, Rajendra – WJ07
Rauch, Kevin P. – WI15
Rauer, Clemens – TI04
Raymond, Kyle T – MJ08
Reber, Melanie Roberts – TF07
Redlich, Britta – RB03
Reed, Amanda – FA03, FA04
Reed, Zachary – WF03, RF05
Reichardt, Christian – TI04
Reid, Scott – WJ07, FC08
Reiland, G P – WI01
Reilly, Neil J – WJ07, RD12, FD07,
FD09
Remijan, Anthony – WI04, WI11,
WI12, WI13
Rey, Michael – MJ14, RE06, FA08
TE06, TE07, RD01
Schnepper, D. Alex – TA10
Schnitzler, Elijah G – WJ03
Schuessler, Hans – RF06
Schwaab, Gerhard – RJ10
Schwan, Raffael – RJ10
Schwartz, George – MH12
Schwarz, Cara E. – MG10
Schwenke, David – MH06
Sears, Trevor – MF07, TI13, WF08,
WF09
Sedo, Galen – MG12
Segarra-Martı́, Javier – TI08
Segura-Cox, Dominique M. – WI14
Seifert, Nathan A – MG07
Semeria, Luca – TJ01
Senyel, Mustafa – FC05
Sera, Hideyuki – TF02, TF03
Serrato III, Agapito – RH12
Shaffer, James P – TJ11
Shen, Linhan – RE05
Sheps, Leonid – WG12
Sheridan, Phillip M. – RA01
Shipman, Steven – TC07, TE04, TE05,
TE10, FC07
Shu, Ran – TE03
Shubert, V. Alvin – TD02, TE06,
TE07
Shuman, Nicholas S. – RA06
Sibert, Edwin – TH02, WH09, WH10,
WH11, RG01
Siller, Brian – FB06
Sims, Ian – MA04
Sinclair, Laura – WF07
Singer, James – WG10
Singh, Vipin Bahadur – WJ14, RG07
Sironneau, Vincent – RF03
Sjouwerman, Loránt O. – RD11
Slaughter, Kai – MJ07
Smith, Houston Hartwell – RI13
Smith, Jonathan M. – TI14, RE08
Smith, Mary Ann H. – MH05, MJ11,
MJ14, TG01, TG02, RF08
Smith, Peter L – RD09
Sneden, Chris – RD10
Soulard, Pascale – RB10, RJ11
Spada, Lorenzo – RH06
Spaun, Ben – WF02
Springer, Sean D. – WJ04
Srikantaiah, Sree – FB03
Srivastava, Santosh Kumar – RG07
Stahl, Wolfgang – MG06, TD03,
TG07, TG12
Stanton, John F. – MG02, TH01,
TH09, TH11, TI15, RA08,
RB05, RD12, RG14, RJ07,
FD07, FE05
in
ar
y
Reza, Md Asmaul – FD09, FD11
Rice, Johnathan S – WI05
Ridolfi, Marco – RF10
Rieker, Greg B – WF07
Rijs, Anouk – WG03, RB02, RD01
Rivalta, Ivan – TI08
Rivera, Cara Rae – RH13
Rivera-Rivera, Luis A. – WJ04, WJ08
Rizzo, Maxime – WI14
Robichaud, David – RF02
Rodgers, M T – MI12, MI13, MI14,
FC09
Rojo, Michellle – RC02
Ross, Amanda J. – MJ07
Ross, Stephen Cary – TB04
Rothman, Laurence S. – MH01,
MH02, MH03
Roudjane, Mourad – TH09
Roy, Althea A. M. – WA04
Roy, P. – TB05
Roy, Pierre-Nicholas – RJ04
Rudolph, Heinz Dieter – MG04
Rupasinghe, Priyanka – RF01, RF02
Ruth, Albert A – RE09
Rutkowski, Lucile – TF05, TF08,
TF09
Ryland, Elizabeth S – RE01
Ryzhov, Victor – WG02
Pr
el
im
Parlak, Cemal – FC05
Pate, Brooks – MG07
Patterson, David – TE06, WF02
Pearlman, Bradley W – TA02
Pearson, John – MH08, TG01, TG02,
TG03, TG06, WI09, WI10,
RB09, RD05, RD06, RD07,
FB04
Peebles, Rebecca A. – MG07, MG08
Peebles, Sean A. – MG07, MG08
Perez, Cristobal – TD05, TE07
Pérez-Rı́os, Jesús – TJ12
Perrin, Agnes – TG04, RF10, FC04
Perry, Adam J. – MF05, MF06
Perry, David S. – RG06
Petkie, Doug – FE07
Petrignani, Annemieke – RI04
Pfau, Tilman – TJ12
Phillips, Dane – FB03
Piancastelli, M N – WG06
Piau, Gérard Pascal – WG11
Pihlström, Ylva M. – RD11
Pineda, Jorge L – WI05
Pino, Gustavo A – TH05, WA01
Pirali, Olivier – TB02, TB05, WG11,
RB07, RB08, RB09, RB10
Plusquellic, David F. – WF01
Pollum, Marvin – TI04
Porambo, Michael – MF04
Potapov, Alexey – RJ01
Pototschnig, Johann V. – FA02, FA07
Pound, Marc W. – WI15
Power, William P. – TC02
Pratt, David – TG14
Pride, Michael A – RC02
Pringle, Wallace C. – MG05
Pszczółkowski, Lech – RF11
S
Saladrigas, Catherine A. – FE04
Salomon, T. – RB07, RB08
Salumbides, Edcel John – MF01,
MF02, MF03, WG08
Sams, Robert – FB04
Sardar, Rajesh – TI07
Sasada, Hiroyuki – TF01, TF02, TF03
Satija, Aman – RE02, RE03
Sauve, Genevieve – TI06
Schaefer III., Henry F. – TH06
Schäfer, Mirko – RD03
Scheidegger, Simon – TJ01
Schellekens, Bert – MF03
Schibli, Thomas R – WF06
Schlagmüller, Michael – TJ12
Schlecht, Erich T – TE03
Schlegelmilch, B. – WI07
Schlemmer, Stephan – MI01, MI02,
RB03, RB07, RB08, RD02,
RD03, RJ01
Schmidt, Deborah – WI02, WI03
Schmiedt, Hanno – MI02
Schmitt, Thomas – RD02
Schmitz, David – TD02, TE06, TE07
Schmitz, Joel R – TC06
Schnell, Melanie – MG11, TD02,
244
T
Tabor, Daniel P. – WH09, WH10,
WH11, RG01
Tada, Kohei – TH13
Takahashi, Kaito – FC01
Talicska, Courtney – MF04
Talipov, Marat R – WJ07
Tammaro, Stefano – TB05
Tan, Yan – WF05
Tanaka, Keiichi – RH07
Tanarro, Isabel – RD08, RI10, RI12
Tang, Adrian – TE03
Tang, Jian – MJ01
Tarbutt, Michael – TA04
Tarczay, Gyorgy – RJ12
Tashkun, Sergey – MJ14
Tatamitani, Yoshio – RH03
Tennyson, Jonathan – MH04, MH13,
TA08
Teuben, Peter J. – WI15
Teunis, Meghan B – TI07
Tew, David Peter – RA03, RA05
Thapaliya, Bishnu P – RG06
Thomas, Javix – TD04, TG11, WJ02
Thomas, Jessica A. – MG14
Thomas, Phillip – RG03
RA04, RA05, RC08, RH04,
RH05
Walker, Zachary – RC02
Walsh, Patrick S. – TD08, WH09,
WH10, WH11
Walters, Adam – MH08, RD03
Walters, Nicholas A. – FE06
Walters, Richard S. – RA09
Walton, Jay R. – WJ08
Waltz, Terese A – RJ13
Wang, Jin – WF05
Wang, Lai-Sheng – RG15, RH15
Wang, Lecheng – RJ04
Wang, Xiaohong – FD03
Wang, Yi-Jen – WH02
WARD, TIMOTHY B – RA09, RG12
Warner, Brian – FB09
Warner, S H – WI01
Watanabe, Kyohei – MH07
Wcislo, Piotr – MH01, MH02, MH03
Weber, J. Mathias – TA09, WH03,
WH04, RG14
Weddle, Gary H – WH14, WJ09
Wehres, Nadine – WA04
Weichman, Marissa L. – TH01
Welty, Daniel E. – RI08
West, Channing – MG12
Western, Colin – TC01, RD10
Westphal, Karl Magnus – TJ12
Westrick, C W – WI07
White, Allen – RC06
Whitehill, Andrew Richard – RF09
Widicus Weaver, Susanna L. – TE04,
TE05, TH03, WA04, RI13
Wilhelm, Michael J. – TI14, RE08
Wilkins, Joshua – RJ14
Wilzewski, Jonas – MH01, MH02,
MH03
Winnewisser, Manfred – TG08
Witek, Henry A – FD03
Witt, Adolf N. – RI08
Wolk, Arron – MI09
Wolke, Conrad T. – TD09, WJ09
Womack, Carrie – MG01, MJ06,
MJ13, RF09, FD01
Wong, Andy – WG09
Wong, Bryan M. – TJ08, TJ09
Woods, R. Claude – MG09, MG10,
FE01, FE02, FE06
Woon, David E. – RI15
Wright, Emily – FB09
Wu, Anan – RH10
Wu, Ranran – MI13, FC09
Wu, Weixin – RC04
Wyse, Ian A – TA02
U
in
ar
y
Thompson, Michael C – WH03,
WH04, RG14
Thorwirth, Sven – MG01, RB03,
RB07, RB08, RD02, RD12
Tielens, Xander – RI04
Timerghazin, Qadir – WJ07
Tokaryk, D. W. – TA03, TA07, TB04
Tötsch, Niklas – MI09
Tran, Henry – TH09, TH10
Tran, Thi Ngoc Ha – RF05
Tremblay, Benoı̂t – RJ11
Tripathi, G. N. R. – TH14
Truong, Gar-Wing – WF07
Tschumper, Gregory S. – MI15
Tsukiyama, Koichi – RI09
Tubergen, Michael – TG09, TG10
Twagirayezu, Sylvestre – WF08,
WF09
Tyuterev, Vladimir – MJ14, FA08
Ubachs, Wim – MF01, MF02, MF03,
WG08
Uchida, Kanako – MH07
Uhler, Brandon – WJ07
Uriarte, Iciar – TD05, WA02, RF11
Urness, Kimberly N. – FB09
Usabiaga, Imanol – WA02
Pr
el
im
Stark, Glenn – RD09
Stearns, Jaime A. – RG10, FB08
Steber, Amanda – RD01
Steeves, Adam H. – FE03
Steimle, Timothy – TA01, TA02,
TA04, RA07, FA06, FE09
Stephens, Susanna L. – RA04, RA05,
RH04, RH05
Stewart, Jacob – TA06
Stoffels, Alexander – MI01, RB03
Stollenwerk, Patrick R – RJ02
Stolte, W C – WG06
Storm, Shaye – WI14
Storrie-Lombardi, Michael – RC02
Stout, Phillip J. – TE09
Strobehn, Stephen – MI12
Stwalley, W.C. – TJ05
Suas-David, Nicolas – MH11, RE06
Suhm, Martin A. – TD11
Suits, Arthur – MA04, FD10
Sullivan, Michael – TA06
Sumiyoshi, Yoshihiro – RH07
Sun, Yu Robert – WF05
Sung, Keeyoon – MH05, MJ11, MJ14,
TG01, TG02, RB09, RF02, FB04
Suzuki, Mari – MI04
Suzuki, Masao – MJ02, MJ03
Swann, William C – WF07
Szalay, Peter – FA08
V
Vaccaro, Patrick – TI11, WH08
Van, Vinh – MG06
van der Avoird, Ad – MJ09
van Dishoeck, Ewine – WG08
van Wijngaarden, Jennifer – MG12,
WG10, RB07, RB08
Vander Auwera, Jean – TB06, RF10
VanGundy, Robert A. – RA06, FA05
Varberg, Thomas D. – TA02, RA07
Vazquez, Gabriel J. – TJ13, TJ14
Vealey, Zachary – TI11
Verkamp, Max A – RE01
Viggiano, Albert – RA06
Villanueva, Geronimo L. – MJ11
Vogt, Natalja – MG04, TG04, FC04
von Helden, Gert – WG01
Voros, Tamas – RJ12
Voss, Jonathan – MI06, MI07
Vura-Weis, Josh – RE01
W
Wagner, Ian C – RI13
Walker, Nick – MF13, WJ01, RA03,
X
245
Z
Zack, Lindsay N. – MA04, RA01,
FD10
Zakharenko, Olena – RF14, RF15
Zaleski, Daniel P. – WJ01, RA03,
RA04, RC08, RH04, RH05
Zenchyzen, Brandi L M – WJ03
Pr
el
im
Yachmenev, Andrey – MH13
Yagi, Reona – WH12, WH13
Yamada, Koichi MT – RJ01
Yamamoto, Ryo – FA09, FA10
Yang, Bo – MI13
Yang, Dong-Sheng – MI10, MI11,
RA11
Yang, Shaoyue – MH12
Yatsyna, Vasyl – WG03
Ycas, Gabriel – WF07
Ye, Jun – MF11, MF12, WF02
Zgierski, Marek Z. – TI03
Zhang, Kaili – RE01
Zhang, Ruohan – TA02, RA07
Zhang, Yuchen – MI11, RA11
Zhao, Dongfeng – RG09
Zhao, YueYue – TG07
Zhaunerchyk, Vitali – WG03
Zhou, Jia – MI07, TD10
Zhou, Yan – MF11, TJ06, TJ07, TJ08
Zhu, Feng – RF06
Zhu, Guo-Zhu – RG15
Zhu, Yanlong – MI12, MI14
Zingsheim, Oliver – RB07, RB08,
RD02
Zinn, Sabrina – MG11, RD01
Ziurys, Lucy – WI01, WI02, WI03,
WI04, RA01, RA02
Zou, Luyao – TH03
Zwier, Timothy S. – MG13, TD08,
TH08, WH09, WH10, WH11,
RB05, RG01, RG11
ar
y
Y
Ye, Yu – TE03
Yeh, S. C. C. – WI07
Yoo, Ji Ho (Chris) – MF13
Yoon, Young – TH07
York, Donald G. – RI08
Young, Justin – RA01
Young, Justin W. – RG10, FB08
Yu, Shanshan – MH08, TG06, WA05,
RB09, RD05, RD06, RD07,
RF02
Yukiya, Tokio – MJ02, MJ03
Yurchenko, Sergei N. – MH04, MH13,
TA08
in
Xantheas, Sotiris – WJ09, RG12
Xie, Yizhou – TI07
Xu, Hong – MF07
Xu, Li-Hong – TB03, WF12
Xu, Lisa – WI15
Xu, Shuang – TA09
Xu, Yunjie – TD04, TG11, WJ02

Abstract Book - International Symposium on Molecular Spectroscopy

Transcription

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